SYNTHESIS, CHARACTERIZATION AND CATALYTICACTWTTY OF TRANSITION METALS COMPLEXES
A dissertation submitted to the Depart Dent of Ch€mistry,
Quaid-i-Azam University, Isldnabad, in partial tulfi llmentofthe requircment6 for the de$e€ of
Doctor ofPhilosophy
InoryenidADdyticrl Chemistry
by
Malihq Asma
D@altmcot ofcbenistryquaid-i-A.ann UdveEity
hla@bad
z0LO
DECI IAT|OIIT1'! s b dit rh.r rhi d.dM qrnbd "ryr,.d,i c aM4bl' .rd
ctuIr^k lddo ot TnB!d., atub c.4r@" ia.nift.d by rri ,' drr,ah E Ecrr.dr r p@' rofl by 'll D.p.nMr of chdlty. (\!i<ri-^m un,vsjry, titnri|d.P.ritu, E srirtins dr ldrm rcqumar ro h. &sd or D,6, d/ Pr{.,qrry in4,d'd..n'',,'d. aEe'4
ll.d or S.dior e $Ftoi$r:
Dr. A,q Xna Rsdr I'h6
,45n
CONTENTS
Achwledg.dG
Chzp@] Irnodudnm
1.1 T}!q of ndnion M.t lc.blytl!1.2 CpB.&dclrdyt1.3 Non4t B.!.d C{tly.a1.3.1 N,N4h.l{dctrltl!r.32 N,o4.l.icdc.r.ly.!l.!.3 P,P<b.lrEdc.rlFrr1.1.21 PtI,P{tEhdC.dFr.r.3 5 N.N,r.r-B!rcd TtuitidM.r.l O!bd3t 3 6 Coub^nid 8...d Tlsitid M.i.l C.ldy.r!
L4 /€y Fqtun. of bE T6iti@ M.td [email protected] ProD@d Mah&i@ of Etlyla* Olig@dizlt'd1.6 T4triqs fd ldFd Aobris1.7 c@rrlt6r Ef.&r hd S.Lcri@
1.8 CopolFdiaijor of Btlryl.nc *nh vlriolt lohr MoDn6usiry Tlssilior Matl Clulyd5
1.9 AiGsdobj*tiBLlo Futudoud@k
Chalra2 E !.rlaaral2.1 M.Ei6L rnd Mctrod!
2.2 PB.dle 16 Oligohai4tio .td Polyndi.ltid rr I 0 a!.ErhyLE Pe.N
2.1 Pr*dw fd Oli!@iatio. .!d Polttdi?,tio .. l0 .h
I
iti
5
5
l0
llt2
r3
t8
20
20
2A-55
t9
l0
PE$E of Erhylac
2.4 Chreniln Corpld6 3l
2.4.\ Sydhcsior2,tuindhyl-N-(l-(6-(quinoxrliD-3yl)pttidin.-2- 32yl)-.rlylid*)b.ffi nninq,Crclr IC-l l
2.4.2 Sy.rhcstor2,tuicinylNll"(6-(quindilir'3-ylh,"idn-2-yl). 32cihylidd€)b.nanininc.Crclr [C-21
2.4 .3 Syntncsis ol 2,6-dii spbpylN{ I '(6-(quinoxalin-3-9hynd'n- 332.yl)elhylidtu)be@imin.,Crclr [C-3]
2.4.4 Synrfilsis ot 2l,Gtrinclhy l-N-( I -(6-(q u inoxalin-3 - yl)p"i diD- 332-yl).6ylidere)b€iaimin..Crcll IC-41
2.4.5 Synlhdisof2,6ninucN{l-(6-{quiDonlil3-ylh}tidih-2- 33
,lFthyliddc)[email protected] [C-5]
2.4.6 Synddiol2,6nicN@N{l{qquimnliF3'ylhyddn-2. !3yD{dylid.rc)t
'ainim.clcl' lc-61
2.4.1 Synd6iof2,GdibmeN-(l-(6{quinonlinlyl)pyridin-2- 31yD-e$ylidfl€)[email protected] [C-?]
2.5 Synthcsis of2-quino*linyl-6-ininoplddire Lieands 34
2.5 .l Ethyl 6-(2-brmorc.rtl) ptrid inc-2-c(boxylal€ 35
2.5 .2 Ethyl 6-(quinohli'.-2-yl) ptridinc-2-cfb.xylat€ 35
2.5.! 116(Quinqdin-2-yl) DrridiF2-yl).lnrlr@ 3s
2.5.4 2.6-Din thyl-N{rlqquinoslin-2-yl)r,ylidi.e 2- 3sy!)cilrylid€relt @nini&
25.5 2,6-Di.ihyl-N{l{6{quircx.lin.2.yl)ptddina2-yl).l!ylikG)- J6
2.5.6 2,6-Diispnpyl-N-{l16{quimx.lin.2-yl)pyridina2- 36yl)edylidenc)-lmninidc
2.s.7 2,4,6-TnmedylN-(l -(6-(quieralin-2-ylhrridine-2- 36yDedylidcn )-bc%ninidc
2.5.8 2,6-D lt!ob-N{ I -(6{qui noxll in-2-yl)ptridina2- 36
,,D.rhylidereIb€eDimidc2.5.9 2,6-DicbocN{l{6{quinoxrlin-2-ylh}ridioe2- 36
yl).|hylidelb€[email protected],10 2,6-D_bronFN{1{6{quirodin-2-tl)p}nditu-2- 36
ylF.hylidm)b.naiail.2 6 Inp@€{t SyndEtic Pd@l r.d lusiblc M@hlDisn in 31
Fming rce!,lprridirc lion 2,6-Dicar!.&oxt?yridb.
261 TnDslomlion in lh. llt$cc of Etunol t1262 TnrfomiioninrhcAb*n@ ofEthool t926.! kol.ti6n of the d,K€lo Escn Inr.nn diile 39
2.81
2.82
2.8.3
234
2.4.5
2.3.6
29
1'
a3
43
a3
,t3
TGnsiomingq-KelcCadoxyhrcConpounds inrorh.coft Aondjng Ac.ryl Poduci.
?allrdirr Corpld6 Cdi.iring Mn d Dmr Ug! !IPd( t-d.tl'yluilircXEiph.nyhios?hirc)cl,l, [C-8]
lPd(dic$loh.xyldiaxtis?.blylthosph'r.)clt, IC-91
IPd(r+hloMnilire)(Firy-lolylphos?hine)Clrl, [Cr0]fPd(rv-mcr1'ylmilin Xris?"!olylpho6phin.)Cl:], [Cl I ]
lPd(3,siichlolMilin.Xrirr-rolylphosphirc)CDl, [C-t 2]
lPd(o{hrmrliExrie-Arorylpho+hiE)clil, lcr 3]
lPd(diydohaylmituXEistorylrhorp[im)CL), lcr 4]
lPdcnilitc)($iphmylphoQhirc)Cl:l [C-15]
[]d(r{hloo.nilim)(tiph.nylph6phinc)Cl1l [C-16]
{Pd(r{hlobmili*){Eiphenylphosphine) Cl,l [C-171
lPd(rv-D.thylailiExtiphaylphoehift ) C11l [C-l 8l
IP(iir.G&ilircxldrhnylthoahift ) cu lcr 9lPallldiun (l) Cospld6 Conrlining Phe@tbolirc .ndsub$iturcd PhaniDe Ligand!
lldcl,(2.9nim.ihtl-1,10-ph.MnthDlincxtis-o-
lPdcld2,9ni&rnyl-l,tGtbMrhbliextiphcDy!.pho,phi&)l [C,21]
lPdol2,9 dindnyu,l0-ph.rntbblift )(tk-r-
[]dcl,(2.9-dib.lhyl-1,1o-ph.DinntDlinc)(Trisp-lolylpholphin.)j [c'23]lPdcl{2,9ijmthyl-1,IGphm nolrc)(Diph..yl2-
lPlrcld2,9niddnt-l,l0'phd htolircXffcycle
Pynnidin.-B.@idc lis.ndr
$ethdi! of 2{hlorNt}aimidin.-2-yD bcurid. [L- l ]s)athdn of 2-medryl-N{ty!ini.tie2-yl) b.idid. [t 4
49
2.10
2.10l
2.102
2.103
2.tl
3.1
3.1.1
3.1.2
3.2
3.3
3.3.t
3.3 Lla.3.)-2
33.r.1
3A
3_4.1
3.4.1.1
3.4t23.4.1.3
3.5
1.6
50
50
5r
52
52
562
&ta2
SyDih.stuol4-ohloo-N-(pyrinidir+2-yl)b.Mmid? E.3lSynd$tof 2-bEmo-N{!trimidin.-2-yl)bcn4nidc []--41
Synrh.lisof 4-r.rhdy-N"(pldmidir.-2.y1) b.nanid. [L-s]
CopolF.riation ofEthyl.r. wnh Pollr Co-norctcc (AllylErhyl Erhcr .nd Auyl Bbni&)SyDrh.sisof (P,OOM.)Pd(Py)Mc Cobthx6SyDth.sn of (PO-OMOH Li$trd
Syrrhclb of (P, O.OMc) bs+t . Pd Conpl.x.r
ChrtucnadonofPoly.thyl.n odCGpolyh.E
chrcniun conDldca coD|.ining Substitut d N-(l {6(qliMrlinl-yl)p)ridinc2-yl).lhtlidcrc) b.ffi iE
Sinsl. C.ysrl x-&y Anlysis
Fomti@ of f .tyltyridift ft m 2,tuidrb.thoxyDyridi*
Prllrdiui C6pla$ Cml.ininS Mir.d Donor Ug.rds
SF.tospn: Clrcctt.tioD
NMR-ADlysis
sindc crylul x-R.y Adlris ofc-8, c-9, cr 3 .nd c-14
P.lhdim 0I) C6DI.E Co .iningPb.NnthBliE&dSu6tiluEd PholphiN Liglid.Sp4tleopi. Cho.t rizri@
Sin8l.4.tsid X-R!y An.lylk
PFihidiDtB.MDid. l-ig.Dds
Pd(PooMc)M{Py) .id BrFtE Pd(moM.)Mc crulys$
58
52
62
6l
4.1.3
4 t.5
4.2
4,2.1
4.2.2
4.3.1
4.t.2
33
E3
83
u
85
36
Ethtt6. OtiSoiaizdi.'. Pobi.natiu.d
Oli8oncriatim lnd Pol}ndialion olElhylcnc Udns cr-
ol4m.riation and Pobmdiaion at lattD ptt$r of
Oligoncriarion .nd PolF.riatid .r l0 .h PEsrE of
Ethyl6. Oligonaization ! PolFdiation with MMAO al
Inne@ of Tdpde Dd [email protected] Oliemdizrion .rd Polyndiztion sitb MMAO ar
Chlr.crdiadoD oi Polyclhylcnt
oligotdn doD of EihyL.c Ucing P!U.dim(U) C.ulysljConlliring Mncd Door Ugtu&G@nl !B.de for Edryl.m Oligomiu rioD
E$yl.& Amopolyreiation .rd Copobmenzdon $insi?O!Ma)PdM.(Py).Drt (PO-OMo)Pd,Mc C!l!t$tsHdoDolyDdiztion ofEin t@ !r tow Ethyt@ FlsuEusDs(POOMe)PdM{Py). (Po{Mc)pd-Mcc.IltysCopo\bdiarjon ofErhyhft wir! N*Pobr CeDonoDm(Al Low Ethylc.e PEssure)
Copolyn.iiaid of Ethyla. wirh N@-Potar Co-monm6(Ai High Emy'.n. PEsuE)NMR Ch@ciarid of Ethyt.rdalyt Edryl Ethd
NMR Ch.nct riz.iion of Elnya. md AUyt BMid.
Comlndo! rld FrtuF Wort
8a
8a
87
37
m
9l
96
100
r0l-102
Dedictl€d to
My Reepected Parente (Late) Whp PavedThie Beeutiful
Path for Me
ACKNOWLEDGEMENTS
Fi^r of rU I would lit io th.nk ny st dGor Prci Dt Anit Bcdslun vh@
tind snid.ft.. d@uEscndt md vdu$I. suga.$im! oD .v.ry 5t p 6.blod ne baccondisn $is work r.d ro ..lidr.n ny rutuE.
I M EaIy thanlii lo Prct iichdd F. Jod.n who* positivc ctiticin
contibuEs ! lol iD tnishi4 ny Fsrch wod. B. taugh n. I'ow to do ft&.Eh, how to
wib dd pr.6.nt profesion.lly, Dunng hy sEy in li! gDlp tne Depttud of
Chenisty, Univesily ol Cni@go, USA, I lonl . lot. Hc encoung.d mc on every step
I grotnrly ectnowlcdgc ny indcbtcdnqs lo Psi w.ma Kaminslf ror r.s4hcollabonlim a sell s io! Fovidin! $c feility of sitrdc cryshl X{y aElysis.
Thants arc due lo PDi W.n.Hu Sln who prcvid.d th. olpotlunity to vork in
nis hb. Th. viSpbus ftinins h hir 8rcup ai lh. IttlituL of Ch.nisfv, Chin*
A"ddm, oi S.,.M!. A.ijing @ntibrd ! lor io my PhD worl
I *onld lik€ to sy speirl dunlc $ Pet Slqib Ali, chrimn, D€Fdtudr of
chdisty, Quidj-AaD Unit.6ity, ldr.h.brd, for his @udging .nibde tud
pbvidinA aU lab f!.ilili.r lo @phL Ey F$eh qo*.
I elly .tpEiat. dE h guid.tuc lnd prd.@ of t r' Dit Munotbrd duing
ny rh.sis @tr ction. I @ lh.lttul ro.ll ny L!chd in iE D.pdr!@( of cltdjslrv,
Qlaid-i-Azn U'ivdrty, I!la6.b!d fot than y.lubl. sl)idld dd hclp to cmplele
ny PhD Esrch a *cll .s dE wilc up.
Words e w iD qF*irg sy v.n.ElioD for sy Espeted Dadr! who
s.dinccd $€n d€sit3 ovd nit., p{y.d fm ny .difietion, end.av@d tor try
benme , faed wilt cousgc all vdlliou! nomh$ dEr c.n slong and ch€rftllv
hk buden of my prodigious and prcdigrl dldi.t
words orc ihldequak lo oxpEss iy hdni.sl iddition ior mv lrdE6 who
nbosmed De wirh uE .v.di*ing rhrdow, of lo!. dDd rffetion and mboldered ne
iD removins the ibp.dimnl! thlr cam. in ny w.y durinS ihis sdrDuous work
I wld liL ro ih.rl dl @nt n of |!*en rd9r of Elt Dr' Atb b.dibih
.nd PDf. Dr. Srqft ali, I t!.!& Hi!!d Edrdid Cdntiso of P.ti.trt tu lL.
Pbjd (PEj4r No. 2o.68/R a Dzslg) .rd |taflddl R!;Eh Surr.fi hit.otiw
PDS6 .n ndn &boltthit &. iDditg ny tE&[ rdl .r i'. D.Pttsl of
Cndidy, Unjq.ty 6f C!i!tro, USA, I .l- th.t* AtdF@Sdm b.tluL of
Tlk ric.l fty.i* Iblr, for fEdilg oy rsDb wdr.t dE l!6't|b of Chdnidv,
chire r{qdqny of Sci.e., E ijiit,
achrwl.dtM! E .ls ib. lo try h@t ticnd* co[..9tr ofrrid rnl.cluiel rtff of $. tr.D.!$r.nt of ClEni.ty, fd tlFh ldnd .tlit!d. .td ddngmm
(lt dha /a$.,
ABSTRACT
ln fiis srudy, difLrnl *ri.r of cllomium ud p.lldium crt lvsls wdc
srdh6ed Chr@iun ([t) conplcxos wcrc s].lh.sizcd contriniq N'N^N niddrE 2_
qlinox.linyl-6-idiDoprndie. S.v.n dilf.Enl li$nds u*d lo PFpaE lh.* oiilvsls !r2,6-dicthylI 2.6-diE Oyl; 2,6dii.opiot l;2,6-diehldoi 2,6_ dinudo;2,6_ dibFno;2,4'
6-tin.lhylN{ t -(61qu inox.lin-3-yDDttid it-2 -yl)cthyli d.nc)b.@ntri n. Thca
.ompl.x6 tcF chrnct riz.d by.l.n i 4lysi5, IDftir.d {..tosop, (lRl $d
sinsl. crysr{ X-ny rMlydi. W}.n tho* .!rly i wd subjdlad io oli8@dianon ud
Do,yn.!iz,ti6 of dny'.t. win modifEd Dcrhyllluninoec (MMAO) ts coqhlv4
rh.y shotrrd hiSh dlFc Etiviry. Th. crdlytic lcrivity EsuI! e iniu.rc.d tv stdic
and .laronic pbp.rti.s oaln. ligt'ds in lh. crbly! Mpl.rd !s *ll a t\. E.cnoD
In onc *dG!, p.lldium {bly$. wd synthasi4d !!ing difi.dl nncd dond
lisrld! (sub6litutd .nilin* .!d subni!&d phosphin.t) Th€ qtrlvla wchdcbi2.d by I& hultinuclor llt, ''C dd rrP) NMR..d shglc crysbl x-nv
anllrsis, 3ho*ing .h,r dE c.rlys$ mlinLin lhc $rc 8pon.Ey in dE $lid .s wcll a in
rhc $lud@ pnc. Siql. crys$l idlys llql.d th.l thce on\56 .tnibn . disloitd
sque pl.N oddidti@ !!.6ct, eund dE Pd e t. Th. {Elrii. .crivity ttudits
Ev{Ld tur rh@ d.lysr. qhibir Eo<tdE &riviti4 for dhyl.F oligondarion
whm rha* w u*d in cobbidri@ virb MAO !s @tdt* I! .mliq si.s. tnp.ll.diun chDla.s *.G pGt r.d @.!iriDs 2,9iiethyll,l0.phcndtholin .nd
dificdr obstitllcn phorphiB ltiph.rylpho6thin., Eiea'lolylpholrhin, ti+n-blylDhos"hiE, lis-Atolylphcahie, cyclohexyldiph.nylphospbinc, dipltnvu_
pyndybboephim, ticrclotE:yhnolpnirc, dith.Dyl (2.n thoit?lEnyl) pb6pliD.l.
Th.s. corDldd wd ch.mLiz.d !y Forid r'$3fom itndd stcto$ory (rr_n),
nultiDucl4r (rH, r'C, rrP) NMR.nd si.gl. cry .l X-ny ldlFit SingL crvltd x_tv
studi* corfim ! dnnd.d .quc pl.dr c@tdiDlion S.on dy All th.$ 6!hs tully
suppon $!r rlEs cdptcxB .xhibt th. s. 8lohcEy in rh. blid !trd $lltio tht*Kcrins in vi.w ln. indslriil iDpo.|!tu. of copolyna, ln..opolyndiadd
of .1hylctu *irh diff@nt pol[ @nolM6 Nch s .llyl .llryl .ih.r &d !,IIy' bronid.
ss invstipt d. Fq rht puao!. Pd(Po.oM.)MdPr) .id bFli4 Pd(Po.oMc)M.
*.!. .nlloy.d. Th. obEiftd copolyo.s r@ ch.nct riz.n by nllnnuclor ID ('H,
'rC, D€PT-135) NMR Md 2D iCOSY, HMQC) NMR. All G!!5 cmlim lnc
incorpor.tion of $c.llyl co{[email protected] i o rlc nlin b.ctbo* oftolycdlyld.
ABBREVIATIONS
Ah@ptuECOSY CofrlrlionsP.cttosopyCp CyclopenldicnylDCHA DictclolexylmtlcDEPTI35 Didonionl.s.nlhccncntbypol4izltidtlnsLrDMSO Din.lhylsulfoxidcDP Dcgr.c of polF.nadoDDSC Dif.EnlialscatninScalorim.!ryEA Eldcnd slyaFr-R Folnd l..r6fm.irn! Gd rP..to@pyGC Gts chbmlogdphyGC-MS Gas chrombrEDhy oouplcd M.$ spc.bnct,OPC Gcl Pcnddon chrcmrqntbY
IR lnfr! Ed st .tosoryIIDPE Hign d@itt lolyctbyldcHMBC H.&ro cld fd.ipl. bond .@LiioEHMQC llct@Etd nultipl. qulld [email protected] r,* dc6ity polrclhrlci.LLDPE Li'@ Iow ddsily DolydnybrcMAO M.dryl.luridarc
MHz M.8rhe
MMAo Modili€d n rhyldumimxwMPa M.3, p.sl,r, N!nb.r.v.Bg. boldul& v.ightm.p M.lring point
Me W.i8ht 6v.r.g. hoLcubr w.i8hr
NMR Nuldm4Elr. EsoMc.
PE PolrclhyL*?hen lh.frnthblin.
pDm Pad5p.lmillionP8i Pou& pd E4!da tnch
rr Fon @npc60€
LIST OF TABLES
Trbl. Tid. prg.
2 I Ubcled diasM of b.llaidc rdp.und! 5l
3 I Cryliallog'apnic dar. Ior C@ndd [Cn] a1
3.2 Oyrbllosnphicdlilfordc!.lhdimconDi.x6 66
,,3 S.l6r.dtddlngrllrrdh.DdDd.lof*ldEdrnrdc 68
1.4 Bond dgl6 (o) ofld{n4la of*nicn srtlcnes d 'ylilrbL 68
r.5 Spc.i6cdMsg6Bo.d!(I) 69
1.6 sdetcd bo'd dhriE (4 12
3,? Crylldloghrhic dab fd @nptd [C-22] 17
3,8 Bond lagth! rnd lond dBls ofcrystrl ofcmpld [C-22] 18
,4.I Oligoh.ri2,lid Dd pobodi4tion $ l.m ofcriylene by IC-l io 85C-4 Crcompld.s witb MMAO
4.2 OlipMiz.rid..dloly6di.tid.tnignantcprsElylcl 86io C-71C\[email protected] MM O
4.3 Co{t|Iysl cr..rim 6rolig@&rlid of .iiyl* ty Peedtd $lc-81
4,4 R{climp.tufr.fdoliSoncdz.nmof.thylmbyPd:conpld.. 89
4,5 C@olyDdiztion of.rlvl.n. wi0' dlyl hEnid..nd.Iyl dr'yl.thd 93
LIST OF FIGURES
1.3 P.lladiun @tldd [C8 to C-l9] 52
3.a ORTE! drwinsofcosPl.x IC'81wnh 6ttul 'llipsids
at J0 % 66
r.5 Prckingdi.S6noftlc ahctuE of@nPlcx [C_8] 6
1.6 ORTEP {tnwingof 6nDLx [C'9]wid! th.dl cliP$id { t0e/6 69
r.? Prcnng d!.sin8 ofobplcx [C_9] 10
3.8 oRTEP <tr.winsof @npLx lcrtl wirh thml.llip$id tt 50% ?o
r.9 Prcking d!.win8 of@idd {c-l ll3.rO ORTEP dr.wins of @Plax tc'lal with thm'l
'tliFoid !t 50% 1r
3.ll Prcld.s di*in8 of coopld IC_ l4l
3.12 P.lltdiuE(2.9-di6.thyl.l,lo_Pnd.uNlin.)(Phorthirc)CL 71
l13 Tt'. ORTEP dnwins ofo.Dl.x IC'221 vilh th'tuI 'llip6oid
d s0 ?6
Figlr. ft|.
2 I Fisch.FPond botda rdtDtq!.
2.2 Par rcrclor lcchniqu. ld hi8h PE$!rc scrion3
!1 Cr(QuimrlliDyl-imiDopyridin.)Clr
1.2 2.6-Di.dyl-N( 1 16_(quinox!l i._3 _vl hrtidin'-2-vDdhvliddc)_
3.14 Prckjns dnsro of conpl* IC_221
]ls Plbnidincb.DanftL P-l to L-51
316 Pd(Po{M.XM.)PY
4l N.mu pbj@nw of Oc Mirc li8!d sLnva !o chl@ ligmd
4.2 TH.NMR (cErctrcDcL, l2ot)oi.lhvl* lld dlvl bonid' (AB)
30
56
53
7a
79
90
4.3 COSY NMR (CDCl,CDCll 120'C)of olhylcrc lnd .llyl bMidc 98
LIST OF CHARTS
clrrt ll{.l.t ltq cbtr of dDitq&! dodly.r.
4.1 NMR&! tudl.q@d. (CDCI$ r!.atq..ds) n
LIST OF SCHEMES
1.1
2.1
2.2
2.3
2.5
2.6
2.1
2.1
2a
2.9
l!
!,
34
nd'Mehbis oto[g@rizti@ of di9@
Synth.ii! of Ct@pto6 (c-l to C.?l
Synth?riE of I{6.{[email protected].'2_yl)crhdoDc tnd ir.inirc co6Fud. win ditrdd rrilirc!
Strtbai! of @tyl p}ridifta 31
sulgc!!.d@cnhinfdrn fodrio of ..ctyl pyddi@ 38
SyDth*i. ofp.llrdiu (tr) @pL,6 Pd(Ll XI-2)C1,, [C-8 to C-19] 4l
Syr lElt of Dol|ldiu (tr) mplaa [C-20 e, C25] a5
Stfihoilof $Mtrt dpyimidiFt nz!6i&@Droodr a9
Syathcsir of eOoM.)Pd(MoXPy) cltly s2
SyDth6i. ofa (PO-OM.)H conpound s2
SyDth*i. of! tcslie Pd{nlyn s3
Mod.of&tiorofit @!t lystM O A,
CqolrBiani@ ofdhylcnc.idrltl alyl Gda 9l
Copolyn riatio of ettyltu eilh ruyl .d!tl cdEr dd .lM boni& 9't
CoDolyh.rizriion of dnyl@ lrd .Uyl cthyl bDEide 9s
UST OF EQUATIONS
l-t
t2l3
lld.?ob,Eiddht F*dofw86PFd@n@ of! r.trc €nl'|!lord.ti.o of AlvLdlg odl'|r
15
l7
Clrtifcale
liil €.i!t set r.r Ddftrh.d .t 0|o D.lddan of ClFfirty, Quil}nAm Uri6ity| IdDrh.d, tb. I!|tft. ot Ch@tty, Chbs Aqdary of Sci.@!,
B.ijirs .,n dF DA.lnndt of Ct@ltny, Udvsdv ot Chlc{o, CHc.so, [!si.,UsA. Tlh{o*ha lott ts !!.|!nbdd.ry otdpL6rE brlvd{ldo! ofPhD
Mtmr.A6tt
,N|RODUCTION
Choptet - IINTRODUCTION
Ttsili@ neril conpldcs b!v. long bdr pbyi.g . vill role it dc 6eld of
caral'sis. ScidtisB dd Es@hqs in d&oir $ w.U .s in ildu*ies e eDsas€d in
stnltl6js !d ch'fub'@tion of tulitio. ndd cdrl.rcs to .r"loE tbc p6sibiliii.s
of dEn ue a qolrsls. As dly midoD 6cdl arlr6Il {tit D'rid, ziIuiu, dd
chDniun) aE biglly oxophilic, Dosl tumddrliad oLis, .slekly polar cc
Eo.oD.B, !d$n 116 calalrsr.. Thc lo*4 oxophilicity Dd 8r.rer ftEtiml sbup
bldM of laE hnsilid n.tal5 conror.d 1o drly tlatiti@ mclals bste dlo nN.tlrqctivc crtalysls for rne polym.nation !! *oU $ copolyndiztioD of elhylcru *idpolar @-nononft udd mild coDdnioDslLr
Trr. inportam. of bosog@us drlysis in pollrMianion dcrions hid
incre6$d lrmendously in lllc plst ld y.rs. Polycthylcn *$ db.ovd.d in l93l
.eid.'!illy in d ICI labqatorr. Wh.n .thyl.n. w* t4r.d with bmldchyd. .t high
t.nFranE r70 "c od nth ps$e 100 Ml4 . wuy pnducr wa obdircd wirh
d.sny of0.92 sm'. Ir {6looh $ Iw d.miry Fl}dlryl4 (LDIE). By 1950,
s|lird oil 0ndi@), ?ninips P.loran dd (d zi*ld.t dE Md Phftt InslituE
iDd.pcn&nlt Epotun Mdrctuir8 [email protected] fd pobltbyltr ar low rdFB$caM prsB thd rhc ICI p!*s. Tn sulrrrl Fly.rhrL& ofr lppblidib rhftiry
or 0.96 gcn I ms caued nisn {Lsiiy poltunyl* (tlDPE) l').
Polyol.fils hav€ b@D us.d !s ih. ndl populd syllhedc polynm *ith at
abul mdkel of bnlioa of dollas, FoltoLfid a€ rhc i.sr.srn.rebpin3 polrm{
irdusFy lr 1l dd:ousn t h:s b.d u.cd conn*i.lly 5in€ lons tin , still it is mrjor
leohnolos/ oli.nEd ro\ber rtrol
Dunna 1990r, bdy rcw noD-n.llll@dc otalysls wft sy.th.sized io
polynsia e$ylae lDmo8hoully !s w.ll rs to @polF.riz. it wiln olha oLnrs
l.l Typ.s of Tntrsiairtr Mctil Cradlnt!Ixe tr|tl|]oru abt$ rrotrn rrod.y c.o tc cLsif€d Mdirs b EiE
ciiE n: $'de, @rp6itioo, !r!. of +plicdid d nd. of.gecgditn Tld! @ tsIsge grq4c h.rdogaea c.r.ltrr (5lit rd. .slyrr) ..d toD€@rB drb,$.TIElGd$gEi tu da ft.B ar6.r hoogmB cdt*.qd.d to $li6(rpo.t d cddr*) de rrom G iml|obili*d.dtG
In rulDoncd er.lysa lte cdrylicdt &tiE 3ut i.@ ir.pdi.d lo. $pDorr @ridltdh.rhrgc,!6e.E&d!oudlyF(ouBytrlt DodioF.ild.$lrischcrelgaFB cdlFri tiomgqFuly odlyzod r!..,lioG c codolhd ditrty by
tirctios .nd les by D.t rirl t6!rpor! b6|u!. difrlio. ofthe r@tad to rhe cdJyrtcrt ocsrr ndE npidy lrl.
Cbd l.t fbw.bn ofclllificiioo ofc.lrlyr3
N@r"al Ni@) . rl/!a of tyF ts{PlbPqH.(co)oNi(rhxl) ui.e si.tlHitid O.fin Po6 6HOP) F.6 LF 06r r!.d to FldE l&lly li|E dyiiaoligoGs. wta LtiL .p..rro. tis.d. sb a ptridiE d !to.?ruE rlid6 &uliliz.4 D.dir6ed SHOP oLb6i Fod@ bign m|edr wighl lilE pot*rrytc I'n-
&!o&tdtt golp slu rd ttn hlty ryl iEiG c E$rirld f6 dr F{.bdio ofnigh
@LqrLr kigh polreytc tq ttl Wtcn sart tstt i: rryrcO tm rt tiginA rn.unhddld otalyst is !.1i€ fu !E oligohdialid ofdhy'ec. Ard{|rgh ttee cdidic
.icL.l oliSon.ri2ltion c.tiltst! rfr huch dolc .ctiv. thD th. n.uEll .iclcl spccic!
wnb P-O ch.lrtca usd in lh. SHOP, th. pbdlcl olison.a, lirc.r d_ol.fr$, !t trysinihr. A tulEll sHoP clrrlysr incorroEring rn ippspntEly b!l*y iryl ahinc into rn
.rioric P-N ch.htiq lisdd should b. c.t.blc of otigoturi.ing d Polyndizif,g
.rhyld. 1o l4.ld nrtcrills widr !tr unus!.lly bnncl*d B[actuE lrr]. In c$. of
BooLlrn o$lyst', dc Pd 0D {d Ni (II) olllyBt c qtionio bcthyl cdDldcr
l(arN-c8)qRFNAr)M(CH:XOElrl' B^{ (M - P4 Nii ^r
- 3,5{rq(CF rlhavins bulky diiiie li9n&.
Prllrdirn $d nicl.l din thyl peurcE Ed po.omEd with li(OElrtBAtt .
It ous lo$ of 6.rh!& dd. di.thyl .dE lddlcl ws fm.d. Ihk ptlbdiln .th6
rddd.6 poltrai2. .thylc*, proDyl@ d l-hdc which Esltt in lhc foddoof hish nolarbr w.ighI Flyr.R whicb e eoDho!. ruEddt. AmipnoDs
poly.rhyl* i! higha b clEd thlD lo*.l|cMi.y polyalnyld. fte bfuclts .tcdfim.d by rrC-NMR rFet!.
Compla [I] E oncd by KB !d 6wtd in 199 ws plsd ro b. m.trcic [email protected][y'd!6r.
t!TIE polyDdirdo @d6* wE do* .r rdioq rlnFBh! (10-60 oC) r.d
.thyl.n. prc$uB (2-6 br} Inc rtula Evalcd th.t th. nt of tolymadziimi.crc.s with ituasitr8 tdFdtrE. Tn .vans. olisondiatid tcltity obscd*.r lot tg oligoM nol- bd'' .r 60 'C .rd 6 ba pEsDE wirhh 6 h. ft wr cmludcd
nDm GC md GC-MS.r$is th oltoDai. Foduc!.ont|ir.6 rMha! oforbd
IXc isoh6 &r.clcd wft of 2i (n - 2- 10) ft.cC$ wnh Mn - 155 (+5).1h. rH-
NMR ecc!| svaLn $!r fiv. dfi@ rtF! of SrouF we pEmt with 2.25(4.1)
M. grcuF id l0 catou. 1.6 conspords ro ch.ir.nd n.rhyl 8reDt€ sd 0.55 ro
ncrbyl or ldser bntuia. Tl* riiidl ndnyl 8dp3 l@ d.l4rd a MGCH{H-
ud iDr.tul crbo.+.Jtotr ddbl. bond! -CH{H- wF !l$ obs.d
al- dd.f!., !*h s FotyL4 8d l-ndd, e olispMizcd i! rh. FB.@of tbb.f@Dslion d qdy.t Thc CC -d SEC @ll! fd d'ee @lring olisoE.s
!E Eihild lo rhoe of ahylaE. Th..6s. oliSoaizrid d.ge. c @t dtiEtv
loscr.d @P = 1.5 ud 2.9 R p.criEly) dd Gull ,{'t rluq of 146 ud 242 !@rdtt8
ro Gc ud 23? rnd 333 &@dil! r. sEc. ln .dditiorl lhc oulysr sdilv i@aie3 tlE
!{l.fnic oligd.6 inio inrdrl olc66 I').
1.2 CFB.sed CrtdystJZt !d Ti @mpLxa cdrli.ir8 M(crtloFntrdi.Dyl)liB!flt vilh DiDoslool
l[lctuF snow bw ol.tu [email protected] &liviti6 a cdrPtlld !o dEit bb{P
ncnllem slogu6 | rr q 4,
CEb!.d.llmim cqnglad hlw b€ po!.d !o b. diw dt.lynt h lhir
cesory tc.6t*r dni. u rdditiod u!.1 doM SDuD .ftha bidg.d du.bridsad to tui! pLir G .iElud.<l. Tl* Cpoit pl.$ r k y El. duing
polyndiztid. Th. rodt ha 3lbn rh.t chMiM @otl@s wnn . ddd gbrp
isi& tlr @di$ri6 .dr4 slD{ hislEr &rieiti.r rhbn k & b !n .@luid thll
bnd8 d cdplqa e m .criw for tdyftndio th& ebddS!<l ^@ na l':r' Dl
Jolly a er nt6cd e .crivity of 14800 rrml 'h ' lq c|lDniM cdrpl* [!I], b.di!8
tn N-pytulidirc p.nd.tn d@r. .lhough 6. tu tio tiB e v.ry shon 14. TlE +inift chMim @ntlqci hlw bcr Ep6n d in rhc lir.atuE. Wh6 tha* cdnDldg
}@ objeEd b IIE polyrsi.rdo of.iny'.i., dEy .how.d Sood crnlriic edvnid
of l70O 8dml '!' *nich n @pubk !o olhd Clibir. 6Epl.s cdt ilirg .C:H!\IM.I sid. m, HoNlc, wlEn .@pLr (M cotui!8 E iniD gEuD
ilcorDd.r.il inro rha quimliE noict , *! !&d r qi.ly4 rh...lirity es ircqtd.SEh ryD. of conpld6 h .&o.6p.blc ro Dolyndiz. Doptl@ io drc ! rn &polyD* with noddE .ctivig. Th. hodg.d chtuion ontLxq [[- IVI with CFN
lig!tr& h.t. b.6 E on d ro polFaiz anybF anro nigb ml*dlr *.idn poly!6,nE* hien tuleuhr u.ighr polymn h.w ! poltdirpdity ildd b tll d8r of Lt to
4. oth6 hiSnly &ds cd.lt5! fd pot n6i..ri@ e dbE b.l@. T!. cntdiuc rlylt M h'viq brids.d Cpd.d lis!& dw bi8!.diviti6 f6 FlyDaizrd@.
IB dfiiwiwr with . DdlFxy gdP .lEscd s &6ttv of llOO 8!dolrlt'bri Dd
*ith . ftlhylrhro sup zOO itmof n \.ttr l' z d'
.4,..,I
gla
ff**IM tvltul
Bun sd @*ortd 6adEiz.d .d cbtsGli4d .hr6iu 69Lx6 driniie .borE li$fl|. TlEy Epdl.n dll rh. *tioi. m.fivl daivdiE
Icp.c(Prr{[email protected](crFr),1, i5 h.lhv.d ro b. thc ..tiw ltccia dwi'g tlF
porFdi2.rio. p's*lI'1, Tn! ick t'@ic ho.!b.ll'e MPk; tull ir .Lo h'8hlv
ettc ld tolymrizrto. of dhyLE io F.du@ lind Flv.lbvl4 041tu ndcutrrcigh i. nodotcly high. wit! l/"- l7od, ltnolr, whic! L hi hd llD ll*DolyclhyLE ptod@ld tt M} h l[i. @ s oliSpddic pt dsr. s@ oblrb.d.
u".e'"t*I'
ryrl tvrl
l3 Notr-Cp B.s€d Crtdystsr3.l Nl-chdrtcd C.tdy3r8
Itu &EbFE or ti6ly rctiE Ni(tr) ud PdCD bs.d qdt$ 6r
lll. scmltyp. (AtN.qRlqr.FN r)M(Cft)l fo. Poltndi4!@ [email protected] i! eu &cnard. Tn t*ri6 of [Pd(M.CN).1(EF.D ttd
A.N<M.)C(MGFN (A!-2,rc.Ht-ih) lidq 100 Dti of .tnvL* pldG irchldofon EolEd hi$ly @rpholr loVdnyhF. Tn PotDd oonircd i. htltv
bn ch.d dd .h. bnehiiS lod !t!d dilEibuio E id.nticll lo lho& obtri*d sh"
thc wclli.6n.d initilor MU] b u..d s qulF
| _-Fll"(). II -*'l
NrtrI
Hilhly bEcb.d polrDd D fd!*d dE 16 Fbv&egd cliDiuliod/ Gintnid*ti@ wnh Frgdnc qtidic drtl i' dEdn& !pci6 lr c@Plax l\qll.ryl nt8,
ln p6p.!dicd.r io th. iqre ptu SorEtry of tlE cdpld sd i'Pr 6oi.tv .1dr
onlb D..itio- fiii rbdld F$n s. Ucrrg. of th. Djd .Ptro.cn of oLfc lr'h.ntrs6 dE EL of ch.in [email protected]. s onFEd lo tl& nE of chdn t afar !'dEsull. in dE fom.lion of . hi& nol4lLr w.i8ht polvffi v.n@ qlimi Ni (lD
conpld.s b.,cd ot uthindald d-diini$liS!& h* bca tt$aiz.d Dd Fov.d ahighly tsriEor,ly.t fd th. oli!@i4tior of .drk c.
tD(l
Ixl tloigsin MMAO ?5t.rlibils u.t?.6t o!:rog tlqufiv of 94IIoiTO hi. ft* bShly.ctirc Ni (IDqrrlyit N D..d for l[. lap.nrid ofcd.6N
Errjng n@ Ca{26, wilh *l€rctivity of liE ddtfis s high s 9a% Er'
Gib.or ud otorlcn n w Gtdr.d . ed.. of [email protected] !dt!ti.dch@iu (Itr) qol/rL dLilbs B4-r.doE 6 /rmlittFidiE ltEd. for
otir.|Eizrrid .!d tot uiad@ of crtd. Pr. Th.$ lis.n& id fi6dn bow of
fi. bdr, .iyl $h.dn|at whicl Fo!.d io b. imFrnt iqiod fd tbc sLbiltrlid ofN'
N- ch.hic mrnt'o n.lrl dtrtyln s *ll x ro obt i! nid tulccdlt*igltlotffiThc b.sic rhEry inrctr.<l in och tyF. of 4t ly.t i! dE pta.. of bllkv g@P.
I.-C!r|. .Fi N-{4-crH.M.)
B]
whicfi offer i g@<t prol.clion for d. m.l!l ccttcr.
chcl.nns lismds podue poly.lhylre disdaing
riivity obuiDed by Cr (III) conplq pOl is ?5g
dictlyl.luninius chloridciEr:Alcl) 6 icliut)r'
Iies rew .atrlysis con6ini4 N,N.
high bol€ular e.ths. The hig!.d
@olrh rhu I in cohbidiid wilh
lxl tlol (R='Pr)
In rhis slsh, lltyblDinio chldi.L lcdv.b @ fodnd t bc EoE acttt
wifi lhos lEcthlysts th.n nedrylalumidrn. (M O) MoEovci, di.tl'vloluDinid
chbndc €t AlCl) is supcrior lo aluninirn *equichloride (El,AlCl EtAlCll) lr0l
Ma.y neuhl and cationic palladim €npldcs cmt ininS N_N biddlite donor
lisDds lr* b.6 sy n*iad in lh. ts1. tt* caldvsts w. used fot rh.
oligonaizrid .nd polyncri?zrim of cliyl*. Tlc nd inbiv.ly sdicd coDpld.s
of lbis t?e aE diinin. md biDtridin @npouds. Tlt gorps of Canrv, TDfinetlo
lnd Jodan E on.d s.vcrrl lr?€s ofPd0l) bb-(Pyfthlv1)ncthan. compldcs i.cludins
(MeC(Pz):)PdM.lNM.rrb),
{Mc,C(Pz)r?dMc(EqO)lr r1l
P.lladiuo (Ir) @npld.r @ntainins cll'yl.ncbndsed Lneitdolin l_ or tis (1,2'r'a_
kElhrdrcqui'oli.yl) nohli4 .na val.y coordin.ting Mniril. or vrlq ({)0lll .nd
IXIVI) hlw bcd rpon.d b caLlya lnc polymcnaion ol norb.nm. b amdpfiolsi
rdnspsEnl pol) (),l-bicyclol2.2.I thcp!2-.n., !r rcon lmpftNF in I E.cton m?diM
consnrins ol a nirtud of dichlfficn5tft, I,2-dicbldob.E* od nit$be@.
AJ"
^.Ce
txlUI
Fur$cmm, tnc Dall.diuD caidb6t [XV] poltinai&! .vcloteDttu lo givc high
nolsul( w.ighl produ.6, Itc D.llmdatid cdied our it nat otllop€nh. quicklv
be.n6 t tlbseMus s tl* po\aM ptaiPit lc.s rim dE elutim Th. Dolvnd i3
iBolublc in conmo. orsmi. slvdts al om knp€dtut, bul dneN6 Erdilv .t 135
"C ir both dccabydDhryhihaldc ind I ,2,4-trichlorob.enc, Ilc DSC of lhis polvner
sho*s av t Tg ot,bout loo 'C dd a brdd ncltins ta$id@ viti @ orel jNl abow
dE Tg od o .nd point of 241 t. IIe poltna cD bc Fe*.d rl 290 'C to girc dd
"te".,],
Ixvl
i sr$I. 6npl.x dd u$d for lho copolymcnation of dlryld. wnh . holhvl as
In 2OOO at.rd cos*6 twnd wi@ inccrring \ N- clEl.tcd Ni
conpldc! wirh I{2 p)ridyD-2-5zcd.r+ (N, N) qT. lig;ind!. ftee caulvds w.E
slbjelod lo lh. polyd.ri4lid of eLhyl.nc in botfi [email protected] ed hct bS.nbus
syslcms. An inLstirs f6luE or ih.$ c.dysls wG lh. f.ct dDl in homoFnous
syslcn, 6 oli8pEic pbducl s obbin d wilh dbiw td&hhg A hciaoFnous
syscn, ln. podu.i obr.itcd vs c hig! nol@llr wish toDDd with 166 brschitrg
In anolh.r $udy tney Eponcd thc sr inmobilizi.S ph.non.Don for bolh cllllvst Fd
Ixvj is
ccsr.lrst wndr lhe stalyst er 6.clionrlized *nn an o_rlt"vl subnitufll ro
p'€p!€ rh. rlf-illrmbilitng c.liyst sha.d higbs rctivilv tor rh. copolytcnanoD
r.rcri6s{16l Nictel and plllidiln oomploxc! containing rxial dmtt4 pvndinc goupr
hrw ben prot.d io b. actiE oltty$ ro podlc. lit6 hid noleula wighr
pol)n n wnn . M, of !p lo 8803?9 ghol r wnh 5 l bnrchctlooo ci6o's Dtl
13.2 N,o+h.hr.d c.telys6variols oationic h.lhylpdl.diun @npl*6 cmt hing r.he cncl.lr4 N_O
ri8lnds hcihybicolidr. (NcJILco:M.-2) d NN_diieD@pvlricolinaDi&.
NCr!|IC(O}N'P.:-21 n vc lei ttndGizd ltd subj.ccd b tlt cotolFdiarion of
l-,l-I".(K"](xv!
""("
txvtrl
[xvfil Ixlxl !) PRr=PPhr [XIxl b) PRr=PCv]
AI 6npl.B IXvl-l(Dq e edt o|tlvsE fo! thc c.poltrdiz'tid of Co
.nd othybm lI{). ftc &livig of 6. c@plqd row.ds Dolvlerorcs fomaiid
da.rc.&s in 0E ordq IxIX>xvIi>XVFXvtnl Tho Gn.thvl subritleDt n t\' pvndvl
rins or rhe NO lisrd hrs s .clivrti.e .ffd Dd coDplds [xvII] od p(xl !tsubsrrniiallv nior. acnvc d4 iltc esp*tiv. conpl.xcs with u6ilulaEd NO ligdds
Ixvll, Evfil. Ho*.6, 6.ndhyl suhdidcnt al$ lad. to ! &da5.d slrbilitv of
@npldcs txwl md txDq Mp!€d ro txvrl !'d [x\,Iu. Th. incEirg th'
ldod.M rl$ irtiles tne &dvnns of conPld€ [XVn] sd IXXI' bd n h$ Id.tiiMbl cfi@i d th. crllyst sltbiliiy.
1.J.3 P,P+h.lated catllyitsThe ononot capability ofphosphines naks lhcn suiltbl' ligtnds ro coordinale
b lrr. b.snion hcr.lt. orc .xmplc of t pdl.diun diPhosPhinidire Mpld is shos:
l,c{ Ar = 2 4,6'Burc6s,
ft lhovs low clhylonc polyn.rizlioD acrivirv This @nplex i5 sinjlf lo Btoo*ndt\
diimiDc enlysi How.H, M. Ni b.ed DghiE c@9lqd showad hl8!a 'd'vle*
F.llmerizslion aolili1i6 rr aa Ncltial ndnvbdladiuD 'hldidt {d crtion'c
ndnylp.llrdiud cmptBcs @iainiDs pttidinc phosPhirc li8rnds v@ ulili'ld fd
elhytcn. oligondi4tion. Thcy show.d lov produclivitv fd cdvlqc oliaom'nzaltn
vidi loF < l6 (nol C,EInol Pd t) ' .trd 3s lo 8s nol% butft 6 nrin Flducrlar'
th. hb hnsirion n tll cmpLres wilh bi&ntcre lilDds cotEinina phdphodr dd
nitoAd dod .:ms hiv. long ler i|e.iS.icd b .xtloE 0*n ctblv{ic &iiviiv ftitcla of lignds is Dani.lldly inleFlnng bectle of lhc ditrerdl tn*fet !s
' rcslll
ol domr and i@pror DbFnj6 of th. :wo c@rdid ng gooti in $' liCFd' D'ailc
th. .xtersiw rcsetcll d. influm of th. ligrnd m lhe c'it$ic ptop€nie ot '
hmition nsl @tld t ltill €ry hatd b PEdjct Fl' R@tly BnNtin and
co*otks rcDo'ted bi(diphmyltrhspnilo)nr.the_rbo4n@c !d(tr) Ni(U) dd Cu(lI)
conDld* and dEn c.brydc &dvjty fd oligondiatio of.rhvl@lal
1.3.4 P-N-P chelct.d cddysl!
various chromiun cdplex.! wilh P_N-P liglrion lBv' b€en u&d as cfiicienl
c&lyc fd ll'. $l€1iE ceriD.rizltion of .$cm ind porvftn'non or stvlw t' 'nctrlhcyolic mecheiln lr.doniDetlv, lincd Eetcrirls art obtoircd for 0E ftthoxv
$bltilnL<l ligmd. Ey v.ryi4 ih. tig$d sauctuF, d' plldtr'rid dislibudo cN b'
confolled io yi€ld branch.d i.on.n
l0
^Pr,",-"d , "",ano"
,,*"^o
\\.//, Rl=M..R2=oM.
IXXrI
Orhd r-N-P nitoS.n bndg.! dtphosPnim [$nds witb odhencrboxvdvl tubd'lulqt
w.re enploy.d fo! lbc syntlEsis of ch@iuD conplq6' Thas conplcx's wd
GDori.d to b. eficidl catrlyds ld lhc r.rftnatjon of clhvl6' Adivtnd of wcll
d.tired prcusos with .x€ss MAO gdoacs dulvric ttstctB &tive ror lhe
rimdizltio! of .$yl@ft I.
ilr[xXI]
r3.5 Ni{,N-B.!€d Tr.nsidotr Metal Crt ly3t!
X6hn and co-wo*6 ctod.d s bnacrtloh.tut chDDiun conPld vlich
snowed r hir! dlylene poltmdianiotr etivitv lt *r! obsc!'d thlt $' clitrtl'c
rcdviry vB dcFndldr lpon dE ldglh of th. cnai' (R so!), ttd dE high61 rcnviv
(? |7 smol'b'brr) *s obrired wh.o usinS R _ dod*vlI"
a r-i7N2'GRcr'6icr
po0rl
ln 2008, Braunt.in's soup Elon d v.ry itidsii!8 cltrdiM {!I) cmPldcs
coni'inin8 ON dd NSN &orDidi. ligrn. Ibd obrvsr '@ !*! lo itctg.E
dncnation of dnyLre larl. SiDilfly, ditrffit niclcl sd t.ll.diun conpl'xcs wR
srd!6i..d, cn@dizn .dd w@ us.d to sdv srbo@ pottnnalio!ldr'
1.3.6 Colnr.r r on B$.d Tnn$irio! Met l C.t lysts
Band and co'eorkds studi.d tho .f.ct of counld hions oi p.lladium
@npla6 @ eIhyl.* polyftriztion. h @ tPonn lllal rh. n6r wdklv
coordimtin8 eion [B(C6F r', podu@d lhc hi$cst dol4ular weiglt or ih.
polyahyLm, *hjla lhc non @rdintting dion, ein.E F.duc.d dE lowd ^ctivirie
of ht lysls tvJll/+l lnd [XxIV-!j lnd the dolaulsr weishr! oi lh. polFe's obbin.d
fron poov{l ard Ooov-bl viry 6ly slishtly, whil. 6. eliviti* olablvst lxxv_cl !r. son.whlr low.t md th. noleula! weight of its polyn.a is sisnificandv lower' Il
'.s f@od rhtt rh. sol4l.r *.iel't of dt totynec poduc.d wiih caulvsrs IXXIV-iI
and DoaIV-bl wnich conbib tne morc weatly cm'niMtjns lnions [BM'(C6F t and
IB(CtrrIl , ircl€dd with iim. wbm. tnN Doduccd bv [)(,\rva] (CFrSOrl mit.de$.ntially .onsbnt with tin.. In addilio! i. ti. iMrd& in solccurar w.i8ht wilh rinc'
lo* ro\disp.Eiti6 *E .lso obwd fo' dE [BM.(qF]rl .nd [B(CdJ]l stslqtt
X)"(,"^*- X)*.* ''*'LPd. tBM.lc.Fsht
lY\YJv{) Exrv-tl lyJuv{l
1.4 Key Features of Late TreDsition Metal C.talystsThr.. key fatuts of tn. orisin.l lniiminc polvndiztion cabivsls @l
(l) Highly.l.clropbilic, carionic nickel ot pllladili carcr
e) IrE ue or nially bulky dniibin ligidds
(3) Th. u@ of [email protected] 6u er ion! or the u!. ofr.a8'nb rhoughl !o prodle
!@rdimtitg coutd ioE
Th. cl.ctophilicity oflhc laL netd cml€t h th.sc c.donic conplex€B cuxs ir
npid nt s of oL6. instio.. nic !e ol bulky li8$d. ftv6 ins.fion ovd chain
rdnsfa. Tho ue of nohcoordiFting couL! ioB ptovides !n lccdsiblc coordimtioD
sft. lor dE itl.@ing ol€6ns.
\2
1.5 Proposed Mechaoism of Ethylene OligomerizationPhoehirc-oxt@liDc p.Ldiun (tr) ardlysrs hlw bc. sv h6izd 8i w@
slbj@led ro cdyhn olisoffiiatioD, lntetcstins f@luE! rboul th6o [email protected] s rl'at
lh.r bar rr dirl !d H incEtio,. TlE oligdd p,lduc€d e lind ol.rB oivnicn
rh. msjo.ily (> ?5%) n odofins wilh ! Schulz-Fldy Etu. of _4 5 !l 25qC. Th'
DroD.6.d D.chi.is ol olig@qiadon b.S,ntiDs vilh n dvl nitil. mPl.x 2b
t(P^N)Pd(CHr(NCArrtlSbF.l( i^N= phosphift{x@iin.), Art-3'5_(CF :c!Hl
invollB inetion of dhyl@ iDto . Pd-CIL' bond to gdd. ! FoPvl 6nplq
{inniadd), wnicn rln bdqrSo cn in Einsfor to icld popvl6. or ftnhd insniot dd
cnrin rdls to yi.ld odd {rnon Nobd olig66.
Klnetics of Mler.lory l.s.rtlotra
I cnJfI rsFPHo4Pd; ' LI
B{Ah).
| 4Jl ]+i#1'**-,t-]1",^,'12cv
1,"*,"*."I tt l
l€**'*/"l|"{",'.1
,^
J*,"**'I Fdl',"'\-,'vR .*
LPdlv,^R: lpoli.^"
1tI'
I
v"i"^^
T
Sch6. l.r: Mehlnisn of altylm digodialio
tl
Follo{ins th. nd ohti! tlnsier d.r4 lhc cal,lrst cnl'B $o pdnllv
pr.,p!g.!d .ycle Th. mrjor pillrdilm contlq's pF*nr und'r ohgomha(ion
(ondirDls !E tl. illqldsonr 6p.oB 2d,nd $.,lkvlcthvlfie sp'cr?s )c Tl'irnnor
dcp.nd on rh. elhylcft tEsE Th. tutuvd nlnbs filquemy van4 'irh
$'c$yknc p&ssuE and follo*! Micht.lis_Mobn ki"rics Analvsis of dal! usins a Lin'
v.oq-Blrk ploi providcs . mdimum Tol of 3600 n'r a1'rhvlac etuition vhich
ooftspoDds lo fie dL of nigalory isediotr of thc itttrn'dirt' p'rhdiun alkvl
dhyl.n @nplq 2. (1* = IO s', AGI = 17 5 rdlhol ' at 25 'C)
Eiiyl.rc oliSoDeriarion g.rfonn d *nh compl'x 3b *hich Mt sim'llr
elecbonic qoD.nies $ 2b bul laclc the dial C_H -Pd itrl'tulid vi'l& micdv
bll,s. Oihd Elatd Pd dpld6 l&titrg ! lubniud rh'l shicld! 6c ditl siL show
onN dindizsdon .ciivit The obsflalions hisnlighr lhe 6i9i6carcc of rh' uial b!l*
Doviricd by ih. lisFd Cspr_H una t 2b lr'l
1.6 Techniques for Polym€r Anrlysis
SFrh.siad polytd cu b. cnmcl.nzc<l bv ruous tcchniqucs su'n 6 DSC'
TGA. CPc.lR, x av difticdoa lD'Nr,R aE-NM& 'rc_NMB' rrr-N\,lR 'h_NM&
DEPIlls), ZD.NMR (COSY, HMQC, HM!C) ctc Mcbii ltd coworks dffiisd
dE bcticity by hyd@lis{fuiatid E .rid. wn'n $t pdt'Miados e ru in lrt
presence or hydssen (l 3 ah)! dF pr.ducri inchd' low moleuhr w'isht sorarcd
aligpn.6 foddl by ch.in rEnsla !o hvdbS'n Th' t*o pos:bl' ctl S@h'ntd
tet"n.rs cm be E$lv.d dd quantin.d 6v gd chodrlossphv !v died atulvsis Th€
bdicitid olDo\d.R E!s. Ii@ .cttclic b 66% n dird (i' ' DoddLlv isocric) lrrr'
or.1 H ":\/
-H\if-ur G!@ic, lYtdioucbc) lcl@'r
Equrnor 1.1: Pobmqiatiot in th. PEemc ofnvdlogn
(l.r)
CC sr€r.iion .nd qu.tiatid wis als r.hi.v.d fot fi. p..Ln4 (r-isw6l,
hcxan G (5 rcsolvcd p.!ks, nfl, .nd nm i$nd co tbL), dd hcrl"ner (t0
ie@d !o srve FjlA te]Ird nd Ft d an.ly$r'
Ba!.d d CPC dab, pobtd pEpaEd bv hcrlloc* coDpld6 rcliatd w'lh
AlRrcl t.d MgRr h.ve ttrsd nolaut.t *eidt distibDrioB wilh n'lv/M' vtlues 'n
th€
Bngc of lcl5. How.v.t, clhylenda_olefi$ .opolvn6 pFPlFd bv ir'6' mElvsa
h.ve rcl.tit.ly Mmw cmPosiiionrl dGiibulions, aD importatl indi€lor ol sin8l'{iE
1.7 Cocatrlyst Effect and Selecdon
PolJaler pbFnica d.pdd uPon nriors fsioB including c'r'l)4i mtuG'
..*tid condnidr (concdlEtion, lcDFntlF' pB!r') and donomet conmlrttion
Th. d.Lly$ utlE .l5o plays r sii6{nt ol. it the polr€thvlcn' pFdcrioD
.4ording lo pE$tt and tuiE rut l densds vtnous arMrd'g caaidt)sts h!v'
b.h dploy.d ovd th. tts fd oligmcn26on 'nd polmdi?rrion 'g' MAO'
MMAO, ErAlCIr, Et ATCI sd o$es.
M€lhylrhDinontre (MAO)
MAO n toenislly hydblyant tituthvl aluniniub (IMA) 'nd
n conlaiDr ii4 TMA
o€ g.n.sl fomlli or MAo n M.fl_o-[AtM.]!4_AlM'r, wh'E n i5 bdwM 5 and
20. Th. turction of ltF .oeblvsl i! rl€ sc,'ndon of a @rdidtiv'lv u@hrrr'd
ctlrlic inim.di.L ftL b s[om *fiem&lllv 6:
6\,6\f6\T$-,"' \}\,-,cH! | \7'.,._""-l
d"' | - 6'.., *ld**l F"-*o,,,,
tAt tBl lcl
Eq!.lio! 12: !rcdrcrion of o tclit onlrr C nob rn' FatdvsG A bv bhol
wirh n.lhylaluninoxde. B does nol hcve a t.e c@rdimtid dt rnd can nol 5d as a
MAo s.nclrtcs tho dih.lhvl con9Lx [B] &on [A] Iha il ab6ftc& t CHr
8rcup nm tBl .nd ptlduc. th. eioq [cHtMAo] TlE @rdi@tiv'lv llBtuiLd
sFoi9s [C] is thc &tial cahltsl lhlt pronotcs lh! .lk'm coorditution drd ienion lhal
a€ na.sery for Dolyndi,lion eti ly. MAO EpF&t$ . dv.rnic eqlilibnDn of
lind, cyolic dd qg! ryp. ols?eis wilh AIOM. buildil8 blck ()O{v_)OMIt)
Doo'l
t,
t)oavrl
A1$ DEsl e both fou ed tle c@rdidrc al cdbr6, lhe l.itd Probablv 8iv4 ns
b hili kwn &idity- $!rctuG of M. tlmino!ft c.!!.e ttE .L$ t a d'rtmin'd
i' dc $lid srllc by th. linglotrystl X{ay ttudi.s such . slnclud t ihc lAlro6l"lctrl
.. ,., a\^_N*'Al'^/\j. ,i, i,r
\1, l,.r..^'cr^'\
powq
Arlnd ttrcm b ben PEPo6cd d lh. t ti. of !!s.F L@(?it d'b All
ibc .vilmd luPPon .n oPdr_ci!. Ettur ths d@ nindl ttloluE ror lh'
dmi'.|,G iD MAO $lulidr
t.p-a-q-4 +-o.p
,Al-o.Al-
txxvuMAO o@pid . 6iqE pqidd s s &iinln|g @rlv6r fot ol'6Fb&t'd
porFajaiios. Thc tbaoluG *@tuol i& idd ofihc MrrO.lge8lia 'nd
dEn pF
snlyrl @ui.rpttu tEtrb illj.6e4
Qu {D chdiql qlcuLfi@ (!o5.d d dE ddftv nftdonrl t[dt) r'wtrid. lrF c.g. s1ncius Eldi* lo lhc litA d ring aEnjEctut's lll Tlc fmflesElll.s intlE dE cddinti@ nmtd of thd 6 ld fot dvg@ dd rlmidm
l6
Th. cig. aDd dtuo l&. tuctoEs hvc b.d popo!.d to roprG.trt tI. MAO
dhi&coE. IE d.vildd ao; lnc sioichioeEic shcoE rclaic" MAo) of [_
Al(cHrp-l ,pp€4 ro b. d.P.D'Lnl upon ttu MAo synthcric rcutc chos.n crr€*opv
vas us.d lo .vahal. th. oolell.r w.igh of MAO aegEslLs with $. findins of v.lu.s
nnging fiom 70o.l2OO gnol rlYr.
'H'NMR spcctu.copy, .l.nard islysis and sturg .xFmenB have
cldly shos that rosr ofPM CIP frms polynaic sctoEs {nn I A(CH'O_] sno.m.! uDn wh@ CHi is Plnhlly Eph€d by hidcr alkvl chtins Tn nodcl_
indep.nddt dalylis in lems of r Zinm-plot givd Mw = 20 l(8Dol r' *hich
coftstonds b aD !68c rt gE of polynaianion D? _ 3l I Aboul 0 8% oItMAO l}rm l.rsc scale t8€:!8Etes qilh ! si& R :lo0A BdalF of hign.t oxvgcdaludiniun
ntio dd lowd alkyl co dr comp.Ed to th. ownll td.nal 'c dn 6sn $'$.ggES c E lMt d conF6inoDlly and llucMllv h.Na chsal' MAO [_
Al(CHr)C-l ud lllminiuD oxid. Al:O1
Oaber.lkyhiiDg co-.rld'5t!Chloiooryan{llniliun coFpounds lnd di.lkvlnlgn'siln ooDpounds Esct
npidly ro sive nne di!p.rs.! whii. slids. Th. nosl pobabl. @ction:
(tr)
E.lrdon lJ: lomaii@ of llkvlanng co<iulvsl
X-Ey amlyris of thc $lid Ptodlcl @nfimed 6. fotution of 6etv ditFscd
Mcclr, wh.n th. Foducb of tho ucnon bcNeen Al&Cl lnd Mg& ueE combtned
*iih n rtllo@e @mpl.F of Ti, Zr or Hf (cidd sutslitlEd mdl@d or lh.n rins
subs.itucd @loerq), ficy fod ehltrictlly tdiv. svs|.ms fot th. potvhsiaton of
.thvlcn. and d-olefins. Howdcr, wh.n MrBul and AlElrCl wcE u&d llone io rctrvale
fi. zirconaeE @nplcr, Eids M!Bn, nor AlEtrcl w!. .ffet d ttr 6e ol clhvld'
rcDolld.rizlioD c.ciiom. polyhd yields nts.d ft@ 2JOO ro I0,OOO g mol I of Z!
conD.riso! wirh MAO s ! oo-clElyd sho*cd lhrt Al&Cl_Ms& coobinatios *q' 5_
The Al&Cl-MgR! combinrtims can ako acrivtt bndM md.nomc conpld4 in ihc
[email protected] Dolyn.nation of Hl.ns Polynqiatio! ofpFpvt'n' vnn &dvai€d
C,HaOnd)ZrcL by ^lEnO-MsBlr
s @.rb$r w'dl ii [al]:tMgl nolrr Etio of 2'3 it
17
50 'C rnd propyl.n. psnill pEsE of O 48 MP. prcduccd Polv?opvld. (2 h vield -200 grnol ra) wirh a n.d.EE &!Ec of ilo@ttcitr iG n.lring poinr i5 136140 'Cl*1. Trinuclar ?d-diinirc lil sd id.uclar DAlladiln ritidbsn hrv. h€n Gpotud ro
prodlc. high nol.crlar w.igtu lind! rblyeth/.rc Fr).
1.8 Copolymenzatiotr of Ethyl€ne with V.rious PolrrMonomers using Transition Metal Crtalysts
Th. iDcorDoniion olpolt gDuls i o r polyoLfn c[ai. innn@t Dattv icv p']vtdpropenics, including ellctt r.sisl!t*, surfac. prcp€tlic! (lainl abilitv, pnDbbiliry dc )
b'ri4 p6pcrli.s, grs p.@bility, !dh6io, nmdbililv, toughnd ind rhmtl
bariei. An imDon Dt fet$r oI succ.sftl c@olvnenadon of polar nonond qnh
.rhylm s r rb'l'ty ro @rFl rh. .no t .nd dbhbunon ol rhc @monon?r In fi'Pl.dud. Anothd inpMl d.teminbr is th. Elitiw r4tivitv of lh. Dotoocs This
depend! on th. otbiLl eturgcs oflha Donm6 ud dEir &srecdvc inteEct'lc d4i'swiih rrr ftdticr orbital of dE ciult€ls. A monon( with a@d overlrp of orbitd
cn.rsica viil th. cllalysl vitl bc ihc prclmd subttalc in polvn.nddon lrtl
B@l(n,n Epon d inpon&t ratuE! d.cdiue the raihil'tv ol
coDolymcliation ol ethylcnc wiih difi.rcni conononqs l@l
l. Thc Elrdw biDdirg sbglh of cdryl4 rnd GrclMs2. The rclalivc itu nim Bte of.lhylcrc and co_momno
3. Thc nG of.lhrd. iMnion inlo neli{t'hon bond
4. Fc.sibility ofclEht loftcrion lner .$vl@e in*nior and oD€ting ofchelar'
Ir 2002. Dr..t Epon n n ult l P, Ol Pd cablvsls 10 @tolvbetnt dhae 8nd
.Ikyl icrylahs gm@ting lild lolynm virh oo_norcna ctorp iMlpdtd in th'
baclbon.. Ac@rding to dis snrdy,. nclhoxy subslitilod €blvsl eas found !o bc nor'
aciiw .nd grodued high nol@llt *.irnr polvsd with nd€ icrvltr' untts
'ncorpodtd 'n
thc hnsr brkbon. of de pobcd mo MoEovs. dts copolvncd
weE found ro b. fon .d try a 2,I-iteni@ nFd. nanlDs Funbm@ tnc eolP
rp@d non-alEmtins .ltFn{O coDolvncoalioD rlclioDt clblv&d bv rbc sam'
lmily of lP, Ol Pd qblFls brsd on Oalkdv ddrariva of
dipfi.nylphosrtinobMnc culfmt tcid. Tbov als pbb.n th. cfi'd of vlD 'g rh'
ilro(y sioup on fi. lP. Ol Ls.nd I1l. moud ot edm buill inb 'opolF
t itu t4l
l3
tn 2007, torddt glo4 cmc up wilh ! rcw 'd.r
md uscd rh. Dftnt csi.lvsb for
th. copolynariatioD oa difi.al polt ndonc6 *ith cinyl@. Th.v 5v rt4d .nunb.r ofprllsdium conpld.! IPO-OMclPd(PyXCIr:SiMor), IIO_MeOlPd(MeXPv),
IPo-O€llPd(McXPy). ThR olalysE v@ round to prodrc. riMr tolv.ihvh.' wnh 'ldw lcvcl of modyl b6.cb4. Thc |H-NMR sp.ch oon6o.d resotunces oi temind
{PCE<E i..., vinyl6d s@ps) dd i.tul (PCH=CHP) dolbl. bdds Potdhvt.nd
obllincd by th.* c llysts htw nMb* av.r.gc noleuhr wcis,tls (Mx) oi6000-19000
rnd PDs in rh. tusE of 2.0-2.9 6 d.cnncd by GPC Aaodrng ro ')C NMR sDeh'
inlemal obnns wd roinly 2.lc;ns (90%) rith sall amounts of 3_olcfiB (3%)'
At a hish p6$rc d o_ol.fs wls not incorpodr.d ltowM !t ?5 p6i (s ah)
vhm l -hex.n. 6 !dd.d ro anvtdc i. d@bl. cos4htion E cdpdd ro 'rhvld';
.ihylm./l-lExcn. cop.bmd w@ oblain d tXe ''C_NMR slecl$ of lhc copobrcr
confim.d n.lhyl .nd butyl lehes. |U-NMR l!.ctr| of dE copolvnd sboq.d a I r'd
2'oleiD cb.in.nd and vinvlid.ne rcsm!@ (H,C{R{| 6 4.76 120qC CDCI,CDCI,)
(Pb6rhirc$lfoEE)P{Me cielysu wd. scccstuIv us'd fo lh'
coFlyncnaton of rltyl vinyl cds .hd .dryld. I1). bjghqsr i*oamdd lcv'l of
vioyl dha wa3 found ro b. 6 9 nol% d 20 psi (l r rd) of €thvl* wirh 60 mol
cononone! concmnition NMR siSmmE fd vinvl tlkvl 'thq fcrhyl.DdCH:{HOR @PolF.E *cc [email protected] bv COSY HMQC "d
HMBC NMR
Th. 3in. c.tdvsls ,iih difi@nl srtslinEnt q@ u*d to iDv'stigrE
copolynenaiion of .$yld. md vinyl nuoride ind found to hrv' $e hisn'sl
i'col'ontio! lc!.I of O.a5 nol% al 240 Pvr rnd 60 p3i (a al!n) PoF Thc itcotponim
or!,n)|fluond. in erh'lem ws onnm.d by H Crnd'F_NvRr'?'(hropvlel
S.n sroup iivstisatd coPolynsiatid or othvl.n. wnn ditf'Enf irreno &Dv ivos
includin8 oxlsd turdmnrili.s, viryl ttu* .'d sn lqtlohc'd @m@n6 siDg
(phosphin+sulfoeL)pllladiun(tr) tysl€D l6tl Jordrn s soup invcsligd'd nDltipl'
inEnior of silyl vitryl .rh.r inb .tt'ylc* balboft usilg (diiini* PdMc' ) spdia
In 2OO?- NoaL cnd @soltcE $oncd thc copolvrdiation of elhrlce w'lh
acryloDitile liins PhoQhim suuooL ptll!(li@ cdpLa'c ldl in tiis oe litu
l9
corolymft rcrc ploduccd. Rrdedly, thcy h.1. utili4d ,.lladiudallrylphoQhinc_
sulfo'.r. crLlyss ro mpolyDaia erhyl.n. witi v;yl ac.l|ra @r' ft.y h!'. .lercD.n.d d.tilcd n*lr.nhtic atudi.s d th. fomanm of lidr Dol)€drylerc chrin usins
lhese pllladium phosphin+sulfonaie caralysis r6tl selectivc .thylmo oopolymcriati@
wnh h.LEhitunclimll coDnotu$ mblyad tt Pdniihjnc hrv. bo tpor&d l1'l .
smc i .cnif,a E$lE h.v. len obri&d usins PllhdiuD 6npl€r.s fdclrloDolyll)dizrion and coDolym.nziior of a md o ditus wirh .thylcrc ltrl sinilirly,
lor copolynonation ofcthyl.no vith CO lt:),
1.9 Aims and Objectivssn. following .r!eB w@ .h. ri4 of thn $.sis:
I To rydh*ie !.w tusition mbl clrily* contlinin8 td md Cr ELk, Firetuhing of th. smcturcs and applicllids in oletu polyh.nanon E&hom sbolld
Foduce D.lyneri wiln @ntolled dehei€l pbp.rti.s
To sbdy sdftrdvi9 rcbrioGliF of rtc d 6cl!l conDlds !! oi.ts!prrrnng $ihblc c.Llysls vi$ ,or.niirlly hth c.bltric lcrivtties.
To study tnc rdclion n.chdisms i,volled in lnc poductioD ofpoly.dylorc and
copdFe6 ofctiyl.n md various pohr nmm.6.
2.
4. To investigai€ rh. .trel of nir.d ligmds in rd .ompldcs d it!. .ihylmoligomenarioD b.nlvid op€dns up i n * disou$iotr oD li$nd erivity.
5. To invdi8lc thc copolynqiation b.hrvid oI [P,O] p.llidiun @mpld.d ror
vlnos P6ld tuMc6 sp€i6-lly rllyt .l!yl edE lnd .llyl bDnidc.
1.10 Future OutlooksLLDPE is pbjecEd to ftnain th. lb!.!l srcwing polyolc,in with oonsumptid
dolblin8 lioD tE y@ 2006 (l? liuion tgrar) b 2020 (34 ttlion k8/yd) ,sdinrLd .nd .xprdi@ Iim lTyo b 196 oI rh. Flyolcin M].er. llE loltndnlnutrctunns G chhaing EFdly in ri.& d.ys. Ncw d.wl@n* rs in lolyndindusEi* is drivd by follovins fcaturd such $ slns.sis of n.w cctalysis, d.5ign and
poduclioD of rew polymcE with impbv.d lnd cortollcd Foprnies (ndible, m@
st@gd, hish LnpcntuE Birblr D.cdds), dewloprlcnr of ra polyn darion
n.lnods Prr. L vid of O. obsF.d pogE$ in rb. Dolynaiatioo ficld w h!v?
plann.d io inv€stigib otha ts$sinon D.trl conpldcs cdr.inin8 N, O md N, P donor
.M d d.n u. fr. b t!.b.d@ ort4'@ Ed ..?orynd d.dol6 ribdit&(!d 6no|1.ffi F.|.rdtg di&6t chdoLtidict lo dlci tt tEloi&ndd.{rlt ! low cod, Fli.liltt , nfddsilili.t fo.ilihy.!d ltaDd llill.d.18v.tor.m!ri.&.urtodboliotaras&dbudidllidF64
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27
qPER'HENTN
Chryter-2EXPERIMENTAL
2.1 Materials and Methods
Ger€rrl CoNiderdloDsAll lfuirll.ti@r 6f air-udd noistuE-ssitiw conpouds w.€ Frfom.d
undd plnfi.d nitogd .tnosdFt usi4 !b&rd schldt klniq!6 solvcDL w.E
dned fouowinc rcpod.d lit ratuE bethods l'r. Mdylaruninox.nc (MAo) *as
Durchis?d iom Albctule 6 1.4 M elutim in lolue* Modi6.d n.thylduhinor*(MMAO) I 9l M in lEp6. ws puEh.*d frm Ar- CoD Die0ryllbninjDn ctldi&(Et:AlCl) rnd ethyl iluminium dichlorid. (ElAlclr) *.8 pu&hs.d tom Acbs and
Alddch ch.nicals. All otbq cidicals includirg 2,6_dicirbdnoryrridi* w@
obbircd cohDeEilllt r'd u€d widbd fidn r purindtion lnlcs sur.d orhdi*
Tolud. ws r.nued ol.r sodiudb@phetonc until lh. lulPlc color atpaEd
.nd ditill.d undd nirtogh prior ro uF. [email protected] ws dittll.d ltdd titrolp'
fron C!H, rnd l.h on sloEd ovd P,Or. badirc M3 dc8!.$d by lri@ fiu-punpcvcl.s and sto&d o!.r moleulo! 3i.v.s Tctanvdofure wls distilled fbn
sodiun^a6ph.non. I'1. Allyl clhi elns, allyl elnyl .thd.rd dly' bmid. w@
purch.ed flm Aldrich, d.ss&n by dF. fl.* puht lnrw cvclca ..d dri.d ovfl
CaH:. (PO, OMtPd (Py) Me ind bt* li* (!O, OM.) PdMe caulvsls weE pEp.'td
followina lnmtoE h.tMs l:ir.
Mcrtins poi ! (n.D) w.E mesEd wnh . disitd .l4lro l!.mrl appdds ft.IR sperra w€E Ecordcd on a Pdkin-ahd Sysld 2000 FTIR spettoncd El.d.nbl
a..lls lw Frlom.d o ! Fl6b EA I I l2 irotmt 6C dlts Y@ Frfod.dwitb a VARIAN CP-3800 94 chbm.logEPh cquipp.d *ith a nmc ionizrid dc|clot
ard a 30 o (0.2 m i.d., O.2t ln liln ihickn s) CP_Sil t CB collm CC'MS drlves
wE Frfon d *irh ! HP 5890 sics n ed ! 8? 59?l si6 Dd &Etor' tha iclds
of olism.E w€E caLulaEd by Eferacing thm wnn tl:c M5 oa solE d fi. blsis
of tlc pGrcqlisiL thd lhe Frs of.tch ft&li@ is apPrc:imdlt proponjonil ro ils
inEsit d @ in th. GC tle. Th. Fldliviry for IiD{ s.I.tu {}fncd d (.m!il of
linerr d.olcfi.s of ill t&tioN/0oi.I anouDts oi oligond Foductl) x 100
23
For elhyl.nobllyl clhyl .th.i, elhyloc/allvl nell)vl .rhd tnd .thvt.n /tllvl
bronid. coDolyncG 8.1 pemertion chr@iiosBphv (GPC) dPdimmls wcic
p.rfod.d on. DolIt.t bboEtorig PL-6PC 220 in5tunmt using l'23_
rrichtorcb.re 6. srvdt (slabilizd with 125 p9n BIII) .l 150'C TIE Plgpl
lotr6 nn.d @llm scl! wd. !sd. All enpl.s wcE pED.Ed in 1, 2 4_
rricblorob.Mn. al I6Ot, Mol@ular wiSht! wds dcremined lollowing GPC u$tg
polystr4eoe s srMdrrd dd iney tE oorur.d fo' lin6 polvcthvl.tu bv uniusl
calibArior lsina thc Mlrk-Houvink p.da.n: K- I ?5 r I0' cn18 r ..d a = 0 67 for
polyqrenc 'd K = 5.90 x lor c#gr ..d ! - 0.69 fq poltdnyLd
I,D Nr,tR aH-NM& ''c-]\lr',{R, ''P-rt\r& DEPTI]5-NMR) a.d 2D-NMR
(COSY, qMQC) spocl ecf Ecdded ot ! Bo*d DMX 300 MH4 Bmkd_DRx_
4ooMltz and Brok .DMX-5ooMgz instls.tt !si!g bdon_vllv.d tubcs al ambFd
|.npcntoEdr.llas.l2lOtusngTMSsdi .turlsl!n&rd.Ch.nic.lshin.ftE
@td.d by EGEM io dE Esid!.l elvdt siea.ls lolv.tbvld. w$ chectnz.d bv
rC-NMR sldtueopy ud sisnDens w.ft confimed bv DIPT', 15
2.2 Procedure for Oligomerlzatlon and Polymerization it 1.0
etm Ethylene Pressure
A Di.n.i.d Fi$hcr Ptu bord. .quiDFd *irh i nlgn tjc bli w chrg'd with
lhe ct$ly$ (20 lrnol; 0.012 g) !lo's wirh 50nL of blu.tu in r slov€ bd ft wrr
a*ombl.d ind artuh.d lo tne etfiyl* slpply line d.d h.rtod ilon8 with mnsllnt
stifin8 for 15-20 nin to F.l€ suE thal d. cit ltd wN cdplcr.lv dissolved Th.
rcEtion nirtle vs nirr.d fd 2 rr ar 30 t &d 50 Fi edtld. pr.$@ Lq n {sc@lcd dom dd dE soNal w6 dlPoEcd Mdnel e0 Dr) ,$ .dd.d io Duip'nEpob4nc. Th. polymd obLir.d *as
'ssi.d *iln D.rbdol (15 nL) rnd chloFfm (l 5
dL) The obuined polyD.r wa3 dricd und.r ucuun oldrgni
]lgrE 2.1: Fi!.hd-!oia BodL Tch{E
23 Proc.drrt for thc Oligon ritrtion .!d Polymcrizrtior ofEthyLtrc l0 rtm PfttluE
Hirn FsG olirpddir.lon -d t lrEizlrid rsiG r* 6i'd od in r2tO mL slllnts src.l.urel.rc ftto.€quitt d *illl n*hsid niEr ed th@os-
Thc a.lq ss dri.n in d own Fior b ah M.nd Frged *ith N/ luu 6eritd TIF cdlF $lotid ir tol4a (30 nLI d. @trlt!...i1tiicE @ 6L) E!rdlcd io rL Ed. undcr clhvl@ lldd.q wnd dE Eq!i'!d lqlpdlE sr4h.{t .ihykfr .r &sirql pt!.@ o0 dr) 16 iftlduc.d lo tbn Edha lLEdm s n rp.d rna lonln by tdli.tiig dE .ihvlo. stplv b th' 14Lr
v*t. A rddl @ur of lhc @lio $l'rid E olLd.d bv . lvriis. lo N$4 dE
olig@dii&tn tn qErd tt rldt J X ad! Ucr il'rir Th' |Ui'itr!slori@ vG r.dinar.d by ldding u HCI .ihnol (t %) elutid TlF polvtur fmtdG fdtec4 slt d w n dhltol, d.in uia t&ud d 60 'C to .Nl.nt wEhl
ftirH d fdly c[&.tqit d.
JO
iElR tlr Pe-Rceior T..nniqu. fq High Pesua R€did3
Dilt Ml tyF! of chrcmium sd p.ll.diln cddyrl! wE pEpdrd lo invetirnclh.[ eldyiic ..rivi9 tor oliS@ianid .nrl polynqiztid of drlyrcm .r wid3cd'ylft pcgc- Ptll.diln c.tdtst w.lb cmplot.d ro.ipl@ c.polynsiziidofa$ylene wlth pold .6monon.R like rl0l .thyl .lhd ed allyl bbmid..
sydndic pre.d@r of th6 ohMi@ ..d Flladim clr,|yns ed thcir
chad.tsrizrioi by vdious sp€Lo&opic tainiquas e rJ follo$.
2.{ C'hroDium CompleresTh. CFconpl.x6 C-l !o c-7 w.rc synrh.siad in epod yi.ld by rcEling CCh.(IHF)r
whh llE @Gpondina ffquircrrlic2-yl)prridinc2-rDdnrfi&n.)b.@ miR in
dichloron.lhn . Th.ir r.suldng sohions ww ooi@itdtcd and diethyl .rh6 ers
.ddcd ro p@lpirir. olt thc !rcd@t3 t'L
0.182 hnol (0.0639 g) of quimrlinyl-imiioplddi* (Ll) ws .dded 0,182 nnol,(0.(X3 d C|CLGHFL. th. elorid v6 riftd rq 2,i h .t @s LmFnie sivi.s.i4 gen s$!.Nioi. 'ft. Bclion toludc w r.duced by .v.todting !id.r vacuum.
Dicrhyl d'.r *c ldt d ed s n $lid w.! oh&ined. TIE dlling pcipiEtes 9sw$hcd rwic. with di.thyl ethd lnd dri.d under ucuuh, Tnc tnal @mpler Ms
I
obbiRi c grn to{da vhicb G crysolian by slor diltusid of lh. $lulion of lh.
conpl.r in didnyl .lhd itrlo ! h.x.Dc layall.
2,4.1 SyDrh€sh of 2,ftim€thyl-N{l{6-(qulooI!litr-3-vDPvridim-2"v1)-.lhylideft)b.@tridlacrcl, IC-l]ftc Cl contl.x *a. tFthcsi&d by dE saN poc.dw a d.sdb.d abo€ 2
GDid.thyl'N-(116.(quimxrlin-3-yl) plddit_2_yl) edvlid.nc) b.lE@Fine (0 132
moli 0.061 r) w$.d:Ld to Crcl! mI (0 0182 nmli 0 041 3) iD CH{lr' Th' sM(onplA $ar obbiD.d w'rh y1?ld of 82"6 IR tx!r' cm ) 2960 Ii88 {t C-fi) l5or'
1475, 136?, l2ll, 1093, 820, 7?o c.lc lot CnHroCBCrNa C 54'1, H 4O' N ll0Fomd: C 54.3. H4.l,N 10.?.
2.4.2 SyDthesis of 2'Gdl.thyLN-(r{5{quhollllu-3-vl)PvrtdlI-2-vl)-.rhylideDc)b€@ritdnc.Crcl3 Ic-21
A sinih [email protected] m .dopt d for dc sFlhsii of lC-21 2' 6_DicdvlN{l {6-
(quinoxrlin l-yl) pltidine-2-yl) dnylidaE) t MnMirc (L2l (0 24 nnol, 0 094 8)
and Crclr Gls)r (0,24 nmol, O.O?9 s) Nefr Escled b fm 0 165 mol (0 039s) of a
sF @nprax wirlr ?3.1% yi.ld. lR ' Dd (I(3r, d_r) 2966' 1589 (v Gl'D' 1485'
14t4. 1371. 1115, 1284, 1159, 1129, 1095, 973, 351, 78l C.lc for CtHr.CBCrNa: C
55.7, H 4.5. N I0.4, Found: C 55.4, H 4.3,N l0 l
(C-l !o ctl
[c l] Ic-2] lc.3l tc'41 tc-51 lc-61 [cr]
RI El CI
H H H H H H
Sc!.b. 2.1: SyDlncsis of ctuomiDm cdtldcs [Cl !o C-7]
2.4.3 Syrthesh of 2'tdltioPropylN-(r-(6(q!iDoxalin'3_vl)Pvndin-2_yl)ethylld.re)ben@i"€.crcl3 lc-31An amlogod precdlE s lpplied fd [cl] w.dop&d to s]ntha.i4 {C'!l'
Sohtion of 2,6niiouo!y!N-(l-(6-(quitoxdin-3'vl) pltidin+2_vl) .lhvlidetc)
b.Mruhin. IL-ll (0.29 hnol, O l2l g) dd CtCIr GHF)r {0.29 mnol' 0 095 3) in
dichloron.$.n. weE slin€d fd 24h Eslting a s€cn poNd€! iD 65 7ol. vteld v nix
(xsr,.ml296r, 1584 (v C-D, las9. 1362, llll, 10s9,829, ?58 Colc for
C,HTCDCTNa: C 572, tI5 0,N9 9. Found: C s7.6,H4 6' N l0.r'
2.4.4 Synthesl. of 2,4,CtriE.tbyl_N{r-(qquimnli!-3-vl)pvridiD'2-yl).ihylid€tr€)benzlrimirc.crcL [c-41
A 23,6-tis.lhyl-N(116_(quinoxtlir_3_vD pvndin-2_vl) erhvliden')
beMnDie Gal (0.25? nnol, o O9a3 d $tutio € .dded ro CClr OHF! (0 025?
nmol, 0.0323 g) in di.hloron thrn. A ligh gtd compld *a3 oblained rit'r 24 h
sriring { r6n t DFibr.. A sEn }owdd in 60.2% vlcld v ftu (KBr, cn ') 2959.
1652, 1646,1608, 1586 (' C=}), 1436, 1'14?, 1363, 1338, 1216, Il!1,1096' 1043.315'
819, 767 cdc fo! Cdi,ClCiNl: C 54.9, H 4 2, N l0 T Foud: C 55'2' H 4 6 N 10 4
2.4.5 Synrh$i. of 2'6diluoro-N-{l{qq!hoxrlin-3-vl)pvrtdi'-2-vl)-€thylid.o.)beo4llnine.Crclr IC-slA 2,tui0u@N1l{qquinox.liFl-vD pvndit_2-vl) crhvlidce) b'@in'
E 5l (0.0?7 mnol, 0 02?9 g) ehdon wa3 odd.d to Crch GffD {0 077 bool' 0 0248
s) in dicnbFt.rh!re ed nittn tu rn A sln g16 @pld *6 dbuin'd wid r'isohrn yield ofr e!.eD powdcr in 70 9% l.ld vn.x(KDtcnr)29e,ls92 (vC=N)'
1434.1368.1212, II28, 1093,1042,976,819,7?3 Anil Calc.ForcrHlclrcrbN4:c
48.6. B 2.?.N I0.8. Folndr C 431,H 2 5,)l,t l
2.4.6 SyDth.llt of Z,6dichlorc_N{l{qquhotrrh_3-vl)pvrtdi!-2-vl)_.rhylidelc)b€rltntDe.Crcl3 lC-61
2. GDichldeN{1-(6_(q!inox!lin-3_v1) pvriditu-2'vl) dhvlid6') b'@Dad'no
tL 6l (O.oO8I4 nnol,0-032 d s !dd.d to Crcli (TltF)r (0 00814 mDol' 0026 s) 'tdichl@Ddhle. A s&en cmplex *!! obdircd. Yicldr (0 045 mmol, 0 025 d 41 % IR
lK!r, cn ): 1067 (D N-H), 1620 (u C - C), l59l O c ' N), 1488, 1369, l2l4' I098' 975
339. 7?0, 639, 5t9, 4r?. Anrl Cdcd. Fot CnHrrCrCrN.: C,45?2; H' 256; N' l016'
Found: C, 45.28; H, 3.08; N, 10 54
ll
2.4.7 Syithetis of 2,6dibroDo_N{1{6(quironlh-3_vl)Pvrldlo_2-yl)'.rhylidcne)benz. nint...c'cL lc-?l2, o D'brcmo N_(l{o{qutmuhn_3_vl) pvndirc2_vl, 'rhvlidftl
b'Munin'
E.?l (0.0053 nmol, 0.026 d w$ ad,ced b crclr GHF)r (0 0053 nnol 0017 d 'n
dichloMcdE* ed sft.d fd 24 h. A gd cot'pld os obbidd *ih ' l'ld of 3e
"/" (O OO2 mmol,0.01ld.IR (KBr,ch),306? (! N-H),1620 (! C - C) 1592(!C=N)'
1505. 1433. 1368, 1213, 1093, 991, ?70, 639, 41?, 375' CnEr'B'.crclN': Atd crlcd
C.39.38iH,220;N,37s lound:C,39.64;H,I 9l;N,841
2.5 Synth€sis of 24uitrox.linyl-Giminopyridin€ Ligends
2-Quinoxalinyl-6_ininatridies tl_l lo L-?l woF pElaFtl follo{itg lhe s'
Ple.du€ as pubtsrEd hy our gbrP pcviouslvlu'
nr""".rl">"r" -*- ."14*;* -$o8-i cq@i d B cHPiqH,r ,,oS
"'s"
S.noe a2t SynnEn ol t-(6(q!inoblin_2-vl) pvridi&2_vl)athMrc ud iB ini6
conpoun& wiih difi@l'dliEs
LI L] L,6 L-1
RI Er F cl Br
tl H H H g H
2.5.1 Etlyl-G(2-bronoacetyl)Pyidin€_2{a.boxvlatea bFmile solution in rc.lic aoid (10 nL) *as.ddcd d$p*isc b a solulion of
.thyl5{cctlpyndiN-2+!6qyLc (6 35 si 0 035 nol) .nd tlBr (15_20 doF} ws
addld in ao.lio acid (20 nL) Thc tucrim nixtoE ws slitrtd for 4h al odrcnEratuE, Th. solv.nB w@ .vrpoEed .nd dE G.idu. Ms .luLd o' I colunn
lsilid-s.vPcl..6eFEroAc (6:l)l A *hn. solid vls obriin d wiln 8t % iel{'d vicrd
2.5.2 EthylqqurrotdiDF2-yl)pyridlnc_2{.doxvlite!thy!612 bomo.@tyl)pyndin+2{dboxvlate (002 nol) was
'ddtd ro '
$rution of 1,2-diphdtl.*di.miE (o o2noli 2l6s) in MCOH (20 n!) kt't o'
pyridirc w8 d:t d dopwie (5 hL) Tne Mcnd nixlut' ws r'fllxcd for ! h vinr
consbDr sidng On c@lrn8. solvctrs sft .\tPorukd rnd fie rndle w'! 'lurod
ol a
col@. lsilict&vp.tul .rlErEOAc (61) ntio] A whiG slid *$ oblaii'd as a
podld$ilh 52 % yi.ld. M.P. lr?-138'c
2,s3 1-(6{Quinorrlln-2-yl)PyridioF2-vl)eth$oreSodiun (0016 nol; Ol8 s) rs dilslwd in 20 nL ol itshlv &iod EloH'
Excc$ Elog wss Mov.d bv vacuun. a solllio ot e$vl-6_(quinoralin_2-yDovnd'n'-
2-ca!boxyla&)(O.OoM nol:2.14 g) iD ndtl|v diniu.d .thI @sr' (lO EL) wrs tdden
droDwis !o EtoN!. Th. E&tion nixturc vs nfluti tor 3h Cotc'ntlcd HCI {20
mLJ was rdd.d rLoDei* to ln. r.lulting bros $blion 'nd
it was tStin ftJlux'd fm
I OL Ana c@lin& 50 nL .fv.Lr wr .dd.d and tll' rqu@us ?nls ws aE cEd eith
CH:CI, (5x20 mL). Th. orsaic phe was wlsh'd si{r 5% Na:COr Gqusn6 $lutm)
follow.n by drying orcr tnhydd! Na?SO.. The slvdts wtE cvapora&d lnd 0t
Esidue {rs pud6.d by .lution ovd . colunD Isilia s.Lh€hl cin'r_E|oAc (8: I ) ntiol
Ixc rGulting producl wa! obEincd a! whito $lid wjth 65% vi'ld M p l l5-l l6 "C
2.5.4 2'GDinethyl_N{r{qquinox.litr-2'vl)PyridinF2-vl)'tbylld'&}b€nze DiDc U-rl2.6-DiD.dvl rnili* (o OO12 Doli O 147 s) vs ad&d io ! elulior ol l_(6-
(qlinoxrlin-3-ylhyndinc_2-tF$.nm (O.Ool2 nol 03 d in lolucE {5o hL)F
Toluenc lulthoDio dcid wG sdd.d in r o6ii\tic asount l-n' ra
E0ucd for l2h und.r in.n .bos?h@ A D.tn_Shrt apPdn'( {'3 $'d lo coov' lhe
fmcn qitct. th. solval ws cv.pmild &t de Gntuc wis 'tucd
ou r colud
hilb. g.vP.i.lhr-Elo^. (8:ll nliol. A y.llo* poducl Ms oboin d with 63% vield'
Mp 142-l4l'C
2.5.5 2,GDiethylN{l{6{qrhoxalin-2-yDpvndhe2-vl).ilvliden€)-b€nz DiDe lL-21
The sydh.lic pwoduE i. rhc sn !s denbcd abov.. 2,6_Dicrhvl anilin'
(o.OOl2 noli O.l?9 d wti .dd.d ro I elurim of l{qquitunrin_3_vl) pvndie-2 vl)
.rnrnorc (O.OOl2 not O.lO g) in rol!.rc i50 DL).Yicld lfr, m D l55156'C
2.5.6 2,GDlilopropyl-N{l{qquiloxilh-2_vDPvrtditr._2-yl)erlylideDe)-b.rDir{De tl-!l'nc $m. poc.dlE ws followed $ above 2, 6_DiisoProrvl milinc (0 0012
no\ 0.246 g) ws !dd.d !o t llqqubodiD-3_vl) tndiF2_vl) 't[@ta (00012
mol; 0.30 s) elution in toludc (50 nL) Yi.ld 74%, m P. 2l 5-216 t
2.5.7 2,.1,6-TrirFrhyl-N<1{6{quimrdir'2_yl)pvridift -2_vl)etbvlldeDe}
beMerimire ILal2,4,6'Trimctnyhnili* (00012 Dolio 162 s)v$ cdded lo t I'(6_(quinoxdlin_r_
yl)Dyrid'ne2.yl)..ban6. {Oml2 hol; O3o s) ebriot in blud (s0 bL) Ir'a
synthctic pdcdrr€ is ln. se. $ D.nliorcd lbovc. Yicld 28%. s P l12133'C'
2.s.E l6Ditluoro-N{r{G(qunordi!-2-vl)Pvrtdile2-vl)'thvlld'le}beDa.imine ll-sl2,6-Dinuoro qnilinc (00012 Fol; o 154 g) wls tdded b a l_(6 (quinoxalin l-
ylhynd;F2-yDtrEn@ (oo0l2 holiO lo s) i' rolud' {s0 nL) $ 0 ellmr' Yield
2.5.9 2,CDi.hloro-N'{r{6<quioonlr-2-vt}pvrtdlnF2-vl)erhvlidene}benzdnin. [-q2,6-Dichlm Militu (o.OOl2 moli O l92 d ts add'd lo t_(6_(quino$lin_3_
yl)pyridiE-2.ylFth.Dqc (0ool2 Fol; O3O g) in toludc (50 tL) !s solv"t Yield
2.s.r0 2'GDibrono-N{1{6{qrinoxrll!-2'vl)Pvddire2'vl)ettvlder€Fbenao.n ne [-1
2,6-Dibrcno aniline (O.OOI2 mol; O,3Ol g) *4 sdded to l_(6_(q!ino!tlin_3_
yl)priidirc'2-yl)crhlnone (o0ol2 nol; o3O d in bl@rc (50 nL) Ti' Emli'ing
proc.dut *as sahd as dc lcnt€d lbdc Yi.ld 26% '
m p 206-20'7 'c
l6
2.6 Improved Synthetic Protocol and Plauslble M€chenhmfor the Formrtion of Acetylpyridine from 2'6_
DicarbethorypyridineForniog Acetyl pyrtilltr6 lron Drqtb.dotvpttldio.
2-c.rn doiy 6-ic.tyl-pytidin. *rt rh. surliDg r.bi.l fd rh. stlth4is of iBtno_
prridin.s Ii *as difiicull to obbit 2_c.Itrelhoxy_6_ac.lvl_pliiditu !s puE pioduct 2'6-
Dieryl prbdin ws ale ilolnted c by-ptoduct .tor colunD chbmlrosriphv' Innitlv,
2-cdn.fioxy 6 t&tyl pyridi.e w& ob6itud in 45% vitld l w.s . chllag' lo obb'n rt
!s rhe only Fodlct wih good )4clde Tlr@foE !n inpov.d sv hcric nelhod *adcr.lop.d ro Fcp.E it in g@d yl.tti
*"7
,E}\
Sch.i.: 2,3: Synihesis of eeql Pvtid'neg
2.5.r The TnIsfortlrdotr ir at! Prs.lce of EtlaolSloicb'oncErc anounls (0 , to o 3 mol) ofsodiun and cthsol vcr' Eouod for
6 L Ddl6 dtugd in 25 nl toll@ An r6.el im hd c@l'd dovt! O l0 Eol' 2 6-
dicandnoxy prddirc (r) in 30 nl filshlt dislill.d .dryl !@lc was odd'd witnin hrlf
an hour under srinins. ft. nixllE wrs Eflu.d tq rdditi@l 6 1ft, dd c@ltd down 10
oon Emp€BruF. Excesivc col'6h1.d nvdleNoric &id (25 rnr' 37o16) a td'Ld
witn siFinE rhc rcsull,nl frixtuE wB tunh.r cnu.d for c p.rjod of 6 h ro conpl'E
lh. @rid. IOO nl of mL' wn rh.@nd rdd.d b diselE th' $lid ds in dE
nixtlr. lo fon r ddk solulion Thc aqu.ous phase tas lhsker vft CH,CL (4 x 25 nl)
for dr..cti@. tn? cmbin d orgmic drr&! w@ s$hcd tilh 5vo 'quoa
MISO'
solution, lillmd rnd thc solwnt *$ .vrpdt d uldd Eduo'd !EsE'
l7
l'-*"t
."ns#*FI
*'l-*ad-\"tf
I cot
*.F-K
-ra"*o
l'-"",I
,-6Qr+r-Eot
oI cot
Hp l\sorl
6.r-a+ &g.-a!.&nhbt dd d."Ot rrtidr
i't
'ftc obtdred nixlur€ was s.Deted by oolunn chDmatoB{phv (Silioa sel, petolsun
clh.r: EloAC = 3:l). fi. nNlly elul€d ponion wts 2,Gdiacelvlpttidin. (9) lhe scond
ponior wis 2qrb.ltory-6- lcclylpy'dirc {5). A mttu aElt is poe.d $e ibni|loof 2.6niacerylprrjdin. (9) l') lnd 2{,rtedory-6{erylpridin. (s) !0r
ln a sroicnioBaEic rsctor {O.l nol) of sodium, ahdol and 2'6_
dicarb.$oxrDridiDe (3, O.l mol), 2$6.thoxy-6{cdylp}ridinc (5) w.s fmcd ( I I 7
I 61% yicld) wilh Eccs of 2.6ni.c.tyhyndin. (9), lc$ th$ 0 50l' with iwo
.quiv.l.'b (0.2 mol) of ediun, erhdol td 2,6nic.rt rhdtTtridin (r. 0 1 nol). l'6_
ectylplridin (9) 's ohrimd 6 Min Dt dlcr {l0 l c; 57.so, i.'d) 2{art rhoxvs'
ac.tylpridin€ as a sid. prcducr (5, 2.7 5 & I 4.2% l.ld) wirn two .nd a half epivrl.nts
(2.r mol) of $diun, .6.nol ond 2,6_dicdb.ltox,"ttdinc(r, 0.1 nol) 26'
,@tylp"idin. (9) vss obitircd 6 tui! prodlct (12.5 & 64 9% vicld) 2_carhl'orv_6_
a*rylpyndiDe wls ! 6id. ploducr (s, L5 s, 8.l% ti.ld). \virh tli@ .qlivllols {0 1 nor)
ol sdium, dl'aml .'d 2,6nicxi€thoxlTyndin. (r. 0 l nol), 2,6'&.thrtidirc {9) *8only ob6in.d i. 12.85 g (66,I % yi€ld),
2.6,2 T.anrformrrtotr h th€ Absenc. ofEtb&Dol
sodiun (0. I or 0.2i mol) ws suspcn&d i! tsily dilill.d tolu* (25 nl) 22 3
s (O I mol) 2,G Dic.tbdr'oxlptridirc (l) *t! dislvad it 5.quihlans ofErOAc (30
nl) iDd *.s add.d with sririn3. IE nixtlE wls dEn Eoux.d fd 4h Atut @li'g .n
.xc.$ snou ofconc.nFrt d Hcl (25D1,l7%) ws d$pwi*.dd.d !'d Enuod fo!
.dditioMl 6h to oonDl.tc tlE ocdon. A dltk elurid was obt in.d, .td lncn 100 dl
wircr @. addcd lo diselv. the elid Diodlcl5. Th. sn work-uP FMs wls
dploycd ro puriry $. troducG. wirh M od I h.t.quiel.tB (0 ?5 nol) or s.dium,
2,6-diccb€rhdypyndirc O, O.l nol) and 5 cqlivlrds ofE'o^c in 25 nl tolud,2 6_
di.c.tylpyridine (9) wr! ilolat d !s ! whn product 01.69,710% vield). wnh th.
stoi0hiweEc Eacrion (0.1 nol) of sodiur, 2,6-dica$ctboxy_Pvndite (r) tnd 5
cauiv,l.nb oi EloAc iD 25 sl tolu@, 2{!rb.t}ory-6{c.9lP}tiditu (5) n,s isolcLd .!r pEdrcl
'n tl I g d@nt (67.3% yicld).
2.6.3 Isolrdon ofth. &Keto Est.n Int.rDedi.t.Sodium (O.l o!0.25 mol)*ssust.nd.d in Felhly dislillcd lohdc (25 n0.2,6_
DicrbcL\ox'"Fdinc (!,22.r & 0.1 mol) was dhslved it 30 nl EOAo rnd rd&d
dDpvisc n da stinins. Th. Gultins nix$c w$ Eflu.d for 4h, !.d c@bd ro 0'C in
an ic./*!ie' b.rh. DituE HCI (l [4 l0O tn) w.s ln.Elna rd^a.d b qu@! ln. Ecrim
39
in an icd*.tcr brth Wiih mployinS thc sanc rorkup p!oc6 r! abolc, lbc psdud ws
pu rifi.d by colunn chrohlogrrphy Gil ic.-8p1, p.ircl.un .$.r EIOAc = 8, I ) wirh orc
.quivrl. ol sodiun (0,I hol), .lhyl 2- ..rb.thdy-6{a.tc!o{dbdyhtc) prtidin (a)
*.3 Eolar.o !! r y.llow oily podu h {i! ss arou aTo% yl.ld) IR (KBr' cn i:
c=o 1?46 cnn. r 7lo cmn. rc-o-c l l4o cnJ. rH-l{MR (6 3oo Muz. cDclr): 8.25 (d,
lH. ry-Hr), 8.20 (d, lH, Pr"Hd), &02 (h, lH, Py-Hp),4.46 (q, 2H,€H,), '1.26 (q,
29, HHr,4.2O (s,2H, H(CH', l.4r (( 6H, CH,(CH,. rrc NMR (6: 7545 MHa
CDCI]): r94.r, 168,0, r64.4, rs2.j, t47.9, \38.7. tX6.2,1241,6r.1,619,441, \42,
witi two sd . h.lf.4uivrld! ol $diun (0.25 ml), di.lhyl 2,6_bi{d_k 10
cuboxyltthridirc {8) {$ isoht.d s r ycllo* oily poducl iD l4,l 8 (46 0% yi.ld} lR
(KBr,or) : c-o l?41.ni, t?o? cnr, !c{-c logl con. LH NMR (6 | SooMHz,
CDCIr): 8.la (dd,2H, Py-Es),7.98 (n\ lH, Py-li?), aj3 (q, aB€Ht, a.ll {t aH,
O=C(CH', Lr2 (t 6H, CHdCIt,), ''C NMR (6; t5.a5 nAa CDCIr):
191.2, r67-5, 151.3, t38.7, 128.9,61.t, 44.7, r3.9.
2.6.4 Tr.trsforIfldg tsKotd.rboxylrt Codpoud. irto ilt.ComrpoDdilg Ac.tyl Producas
Th. tr@nl!.t.d HCI (20 nl- l?%) ws r&cd drop*ie b .lhyl 2{r!.doxy_
6-(d-k b{.rhdybt )p}riditu (a, 0.04t nol, 12.0d. Th. 6ulbg olulion w Enu.d
for 6h, rl'cn ,.h (loo nl) we dd.d. CH,Or (,1 r 25 mU G $.d !o .fut dE
orsnic @tDpoun& lnd thc co*nntdd ltd Pn6odd gtw vuy 2{&!.dioxr_6-
lcctlDrridii. (5, 7.ll & 78.6% yi.ld). Wilh d* em. PrE duE, dhyl 2,6_bis{!-lcl}
artoxyhlcbrtidic (8, 0.04t nol, 13.8 !) wrs usd to fom 2,finc.tylpy.dinc (9)
(5.33 s) i.ld 80.l% It'
2.? Pcll.dium Complexes Contrining Mixcd Do[or Ligatrds
PdCh(CHf|0: {1.29 g, 5 nmoD w6 dn$Md in dn d r@bE (20 d'l-) in ISchlok tub. und.r ritog.n. A $lution of Eph.Dybnos?hie (l 3l s, 5 htul) qr!dd.d dopwi$ b rh. ldCL (cH:cl9: iolurion, Th. ErclioD nixruE w.i Enux.d fo.
o.5h lloDs will: cotubnr stitrin8, A lidir yctlow pMipit L w4 oblin d, Thc p@ipitrt
wls iltcr.d and m$.d twic. wilh dri.d EloH. It. !@nd tup d cqurvrldt rnouDl
oi N-m.thyhnilirc (0.5! & 5 d6ol) w$ !dd.d dbpwis. lo a
tPdcl,(CHTgN)(riphdylphosthi*)l susFision iD cHzcl, and Enuxcd foi I h A ddonnsc slutior w!! obtain.d. A cr'€lallin Foducr ms obbircd stut slow *.Porotifl
oi fie solvcnt rl rcom ldpdlure.
pdcr,{cH3cNr. (H3c tr}-p -ffi,-(n.c$eii"cc".(r1
6a^, RNN_at l)(12)Y' v"
HiC</ \FP-Pd-NCCHI +- 'J3 ct THF/lhr.iux "."S,"-!1,-ngi
Ip,rP - bli+d4btPh.vht^4 Dctu- a$brqteb.sch.o. 2-5: Syntlcsis ofP.lla.tiu (!) cmrl.x.5 r(Llxl2flr [C'8 io C-r91
2.7.r Pd6r-Eclhtlenil,n.Xtripbelylplosabr!.)Clt, lC_81
Th. [email protected] fd rhc D;r.plstion of C_3 i3 dE eo. I d4db.d .bove
PdCL(CHTCNI (I 29 8; 5 mol)j liphcnylrhosphitu (l 3l g s mnol)i lr''m.Ovl.nilift
LO.)J g. t rnol) Yr.ld 33% m.p.. 14?-149 oC lR ry€', cn ) datr 3417 3387. tl2
432,320,259. H-NMR (6: l0o MHa CDCI]): 7 39_7 72 (', ls4 CtrHsl)' 3.08 G,
Hrc- of CtHtlg. 6.42- ?2s (c.E6N-) . DC-NMR (6: rmMll4 CDCIt: 24.t (CHt of
c7H!r.0, 127.9'r l,r,8l (crd'JP), 126.9- t 28.8 (C,Hrlo, ''P-NMR (6: 3oOMHA CDC!]) :
29.9 G, PPht. Ann. clHi.o,NPPd: cllq,i c: 54.82; lt: 4 42; N: 2 56. Folnd: cr 55 21;
H:4.93iN:1.01.
2.7.2 lPd(DlcyclobexyhDir.Xtrb-p-tolylpbosphh€)Cl'l' IC-91
Th. r@.<t$ for lh. Enlncsi of C_9 is 0'e .m. s d.&nb.d abore.
PdCl?(CgrCtOr (1.29 s 5 Mol): Di.lrclohdyLni@ (090 g 5 mol); tisr_
rolylpbosDhina ( L52 g: t mot). Yr.ld 86 t6. n.p., 23r-285 qC IR (KBr, m r) d'b
3341,3265, 516, 142, 326, Ns.' H-NMR (5: IOOMEa CDCIr): L64 - 2 98 (CtrllaN_)
'1.O5-1.26(n,12ll,C1B2tr-),2.12 G, gH, CnHnP-). 'rC-NMR (8 300MH2i CDClr):
25.r-5s.E (cnHDN-), 21.6 (cHt ofc!r|l,P), l26.lt{0.9 (crH,P-), 'rP-Nr{R {6:
3O0MHz; CDCIj): 29.62 (r, (proM)rP). Arl. CllLChNPPd: C.lc. C: 59.69: H: 6 69;
N: 2.tt, Foud: c: 59.,11: H: 6.57:N: 2.49.
2.7.3 lPd('-chloromfln.)(trlr-Folylpno.p[h.]Clrl' rcn 0l
PdOiCHjCN! (1,29 gi 5 mol)i fthlo|@ilirc (0.63 8;5 mol)i tri&A
rolylphoQh'i. (1.52 8: 5 ml). Yi.,td 84%. h, t., 25i-25? qC, IR (x!r, o') d.lt
t,rot, 3382, 5r2,,r,a5,330,263, |U-NMR (5: 3ooMga CDCIr): Lls (r, lH, NE),6.97-
?.28 (h,4H, C.fi.ClN-), ?.!3-?.59 (!L l2H, Cr'H,rP_). 2 '13 (t, 9H, CHI of CTIITP)
tcNIto, (6' 3oor,ok cDcl,) 2l,5 (cfirofc tap), l2J,!128.8 {qn cN-),129.8-
1.1.6 (cnHrP), ''P-Nr'ts (5r 3oorvtrlz; CDCrtr 29.5. G, b-r.lylhP)- Arl.CrHrCljNPPd: Crlc- C: 53.la; H: :1.31i N: 2.30, Foltd: C: Jl 66; H: 4.85; Nr 2 l I
2.?.4 IPd(N-ncthyl.DfiDc)(tir.etolylpho.pblo.)Cl'1, lc-lllfdcldcflrcN): (1.29 !; 5 ml); x-nanyhnili* (l ll $ 5 ml); ti.?'
blybn6sphirc (1.52 8;5 moD- 88% yi.ld. n.p.. l5cl58 t. IR (X!r, cdr) d$:1412,3!a5, 5r1, 419, tt2, 211, h.l.DlR 6: roolrclz; cl€lr) 7.2G7.56 ln, l2H,
cnHnP), 5.1I (x cHr ofGHrN-), 2.3? (!, 9H, IIlc- of CnsnP), 6 68- ?z) (C'HN)
'rC-NMR (6, 300MHz; CDCIj) 21,50 (Clty ol CngrP), 2a6 (Cfir of CtgrN' ),
t26.4rr28.8J (CrltrN.), 128,91n40,49 (CrHd-). rrP NMR (5: 3OOMS2; CDCIr)
29.?8 (., GbrylhP) : Anl. Crli,CLl.lPPd: Crlc- C: 57.01; g: ,1,9?; N: 2.1?. Fond: c:
5?.42:B:5.58:N:2,10,
2.75 lPd(3,tdlchlomr lrcxir|r-p-tolylpho.ptlr.)Crrl, lc-r2lrdCL(CliCN): {1.29 s: J Eol); 3,tnichlo|uili* (0 81 s 5 mol); Eis+
rotlphGphinc ( Lt2 si 5 |lml} 8l% icld. n.p. 299.301 t. IR (KBr: cn ) d.tr 3417,
338,r, 509, 423, 32?, 255, 'll-NMR (6: 3oOMHt: CDCIr): 7-22-? 56 (rD, l2H, CtHnPr,
2.38 (1 91, CrHrP-), ?,1!- ?.20 (E, ,H, CrHrClrNt a80 (1 N-Io. "C-NMR (6:
3OOMHa CDCIr) 125.G128.9 (CrHrClNj, 129l'l{1.7 (ClItrPr' r'!.NMR (6:
looMn ; cDclt: 29.6? (a (Pn MhP} c,sacr.NlPd: ^$1.
ctlc. c: 50.30; H: 3.9ri
N: 2.I ?. Fobd: C: 10.79: ll: 4-42: N: 2.66.
42
2.7.6 lPd(d.hlororliUftXtris-AtolylphospbiDe)Cl1l, [C_l3lPdCI:{CHTCN) (1.29 s:5 mol)i @hlorelili'e (06r g; t snol)l tii?_
tolylphosphin.{1.52g5nDol).?s"/oyield.n.p.261_263"C.lR(Krtchf)drb:3412,
3378, 5O?, 4s r , 322, 260. TH,NMR (6r IOOMH4 CDCIr): 7.29-?,?l (n, l2H, caHrl_)
2.42 G,9H, CHr ofCiLHrP),327 (s, IH, C6H6CIN ),6 ?9_7 39 (h' {H, C6H6clN )
'rc NMR (6, 3ooMHa cDctr) 221 {cHr of crHnP), 126.2_ 1294 (c.ll.clN_),
r29.6-lar.2 (C,g!P-) ''P-Nr'fi (6' roOMHa CDC\), 29.11 (s, (rlblvl)rP) Anl
C,HrclrNP?d:C.lc Cl 53.14;H:4.11;N:230.Ioud:C:53531H:4 l8iN:262
2.7.? tPd(Dlcycloh€xyhmin€)(tri&anolylPhosphir€)cu, [C-l4lPdClr(CHiCN) (129 s; 5 nmol); Dictclohexylanin. (090i t snol)i lris{
roryrphd,phin. (r.52 8i 5 moD.7?%yi.ld. M.t. r l o-3 r 1 'c. IR (rcrpn ') &b:3347,
32?0,5r). 439,328, 261 |H-NMR (6: lOOMH2i CDCI': r 6?-2.38 (CTHDN ) 6 9&
'7.20 (n, r2H, crHnP-); 2.59 (s, 9H, cnH!P-). :rc_l$'lR G: looMtlt: cDclJ, 24.&
55.3 (cDH,N)i24.! (CHr of CnHnP)i 125.8_139 0 (C!Hr?_) rrP-NMR (6:300Mla
cDclr):29.31 G, (orolyl)rP). AFLcnHraclctrNPPd calc. c:59.69; H: 6 69iNr 2 tlFon.d C 595ltH:661N:2.30.
2.?.8 lPd(ADillne)Gnphetrylpb$pli!.)cl'l lc-lslldcl (CHTCN) (1.29 g 5 lmol) .nilinc (0 46 s; 5 mol)i iirhcnvlpho+bite
il.ll g; 5 nnol). 7O7o yicld. M. p. ls3 'C. IR (KBr, m_) <tab: 510 (Pd'!0; 3220 friH). C,]c. C 54 o; H: 4.Oi N: 2.6. Fdnd: C: 54,0i H: 4.0; N: 2 5.|H-NMR (6: 300MHa
CDCIr): ?3-7.4 (m, l5H, CrrHd_); 6 79_750 (C.H6NH ) . 'C_NMR (61 300MHz,
CDCI]): 128?-134.8. (CrtHrl); 126.2.]281, (CiH6\N ) ''P_NMR (6:300MHz;
CDch): 296 (!, CnHrr?) AslaaHnOlNPPd: Ctrc C: 5421i Hi 398; N: 263
Fould: C: 50.19; H: 3.?l; N: 2.10.
2.?.9 lPd(r{hloro.niliDe)(tdphelylphsPhtre)Cl, [C{61PdCldCllrCN) (129 g; 5 mnol); ,r{hlob.,iliE (06r gr 5 mhol)i
riplcnybhorhinc (l.31 s;5 nnol);75% yi.ld M p 269 "C IR ir'Br' cmi): too (Pd_
N); 3235 (N-E). C!lc. C: 50.8; E: 1 7; N: 2 45 Fou.d: C: 50 4i H: 3 55; N: 2'8 |H_NMR
(6: 3OOMH,. CDCh} 7.1_?1 (PbtP)i 6 8_? I (m, 4It C.tl6ClN_) 'C-NMR {6: 3oOMHZ,
cDclt: 123.1134.9 (CtrH'tP); 125.61291 (cdl.clN_)i 239 (3. C'*I|IP)
A.al Cr.Hi0CIrNtld: C.lc C: 50 91; H: 1 56; N: 247 Food: C: 50 51; Hl 3 17; N:
2.0t.
2.?.10 l?d(P'cblorodilir.) (rrtphenylpho'Phin.) Cl,] [c-r7lPdClr(CHrCfl), O.29 ar s mmol)i ?{hroEanili.. (063 s; 5 mnol)l
triphcnylphosphinc{1.31 & 5 nnol),7l% yicld M.p 279 "C rR (KBr, cn )r 502 (Pd_
N)i3449(N-H). Calc. C:50 8; H,3 7rN:2 45 Found C:50.7:H:3 3; N:2 4 H_NMR
(6 3OOMUZ, cDclr):72-77 (CrtHBP)i125 (N}l):6 3_70 (C6H.Cuq "C'NMR (6
,OOMH2, cDcrr): 126 r l2?.9 (C6HrClN-)i 128 1_134 3 (C,dBP); 29 1 G, CIHBP)
Adl.Cr.HrrcLNPPd: Calc. C:50.9t; H: 156; N: 247 Found: C: 5041; H:3ll; N:
2.21.
2.?.ll lPd(methylanili!.Xtriph.trylpbodPhiD.) Cl:l [C_r8]Pdclr(CHTCN)r (r29 s; 5 nnol); ]v_nahylsilie i053 3; 5 nnol);
triphc.ylpbosphin€ (1.31 s 5 nnol).77%yi.ld. M.p. l4s'C IR {KBr, cn1: a92 (Pd_
N)r346J(NH) Calc. c: 54.9r H: 4.4; N: 2.6. Found C:54.8iH:4.4; N:26rH_NMR
(6 3OOMHZ, CDCIr): ?.3-74 (CL|Hd)l 125.8_1286, (CrssNN_). "C'NMR (6
3OOMHaCDCIT): 126.1-123.?{CrHlNIIr; 34,30G,CEr, 1239-13a6(C8EBP);291
(s. C !H f) Anal.Clglcl,NPPdi C!lc. Ci 51 02i tr 4 25; N: 2.s7 Folnd: C: 54 ?9r H:
1.97;N 2.30.
2.?.12 lPd(lttro- ilir.)(trlph.lylplosPhire)Clt lc-r9lPdCl,(CIIrCr') O.29 s 5 DDol)i ti@ilim (0 69 g; 5 nnol);
dpn.Dylpbosphire (l.31 s; 5 nmol). ?5% y'.1d. M.p.165 qC tR {KBr, dr):489 (Pd_
N; ras9N-H} c!lc. c: 49.9s; H: 3.50; Nr 4.36. foud: c:49 72; H: 3.39; N: 4 r?. rH'
NMR (6: IOOH?. CDCL ): ?.1-? 7 (CrHd); 4 4 (NH-); 6.626.64 (C6ItrN)O,) 'C_
NMR (6r roOMHa CDCI]): 152.5 (tlN-C) ; 1363_la2.l (Cd{5N:Ori 126.n351
(C fH JP) 29.2 G, CtrHr iP). A'aLClHsClNrO,PPdi Cllc C: 49 93; H: 3 50i N: 4 86
tolrd C !q5-, H 2.1_:N.4.12.
2.8 Palledirm (II) Complex€s Conteinlng Ph€n|nthrollneand Substituted Phosphlne Ligends
PdCIr{CErCNl (0-25 g l.O onol) *ts dislrcd i. Cn Cl,- A 2J_
dim.rhylpituil@lic (ol 3, Lo lml) slllon ru tdd.d dbp vis E$ltin8 v.llo*D@iridE. ItE l@!o nntlE v!! ltiftd for 5 h lo cdpLc lhc @do. Th.
oEciDibt Ms filtdd ud dricd undor vrcu!ft. In I letd s:€P (03 & l 0 nhol) !Trildio blylphosphin. slurion r!! iddcd drop wis io. [PdCIdCHrCNX2,9_DMP)]
slsp€rsion it CHrCl,. Tn rudon ftixtuc {s h.&d b 50 oc for 3 h E llins . dt*Ed 6lmd soluion Th. $l!. qd crPor.Ld on ! rctaty daporltlr Tlc pbdlct
was pFoipidld by.ddition ofpetol oths (78% yi.ld). M P 290'C.
€*".
P,R1{ l!4!+ -rilRt{ = Tnph.nyltholphln , Tnedrolylphosthinc, Tris-m-lolylphorPhinc, Tris?_
lolylpholphift, Cltlohdyldjph.iylpho$iN. Diph.nvl'2'pFdvlPho€PhineTricyclohdylphdrthin., DiplEnyl {2-mdbryph.nyl) pnoslhin
S.n 8.2.5: srdhBis ofpdLduE (LI) cdpLB lc_20 lo C't51.
2.8.r lPdctr(2,tdtm..hyl-r,rGphelrnthroDmxtrilo-tolvl_Ph6PliDe)lIC-201
?dC[(CHTCN]
2 (C-Ii, aliphrtic),
712, 563, 533, 431,
28a?(Gr! Aliphltjc),
46l.rH,NMR (6: 3OO
2,9-dimernybh.mdslirc (0.2 3, lo(Powdd, cb '): 3054(C-H.
^!u'tio,1588. 1562, 1444, 1160, 1132, 803, 749,
MHz, CDCr! 25qC) 2,3 (., 9H, M.'
CHr .,\rdr. IPdc!(cH3cNh) ""'"'- fYi;o'i"""',','^,', ril
cH: vcx,
lhosrhitr). 2 35 (s, 3H, Me Ph.Dntl$lirc), r.t6is, lH, il,[email protected]) ? rG
'?.5r (b, I2H. ,r.-,v, Phoehir.), ?.58 (d, lH, H', .F 8.3H! , Ph@ndmlite), 7 72_
s.l (m, 3H, H' '?, Ph.mdmlh ), 8.r5(d, I H, lr, F 8.lHa Phdrnftolit.), 8 58 (d.
lll, I{ J= 8.tHz, Pb.nantFlirc).'rc-NMR (6, ?5 MH4 cErclr. 2fc): 216(3c CMe'plBsphin.). 27.9(lC, C, M.Phd.Dthslind, 284(lC, C, M€_Pn€fu$roline),
rz5 r, 125.3, r26.0(3C, A!or!rio), 126,9 (3C, Am.nc), 127.6, r219, rlAr,1242,
123.9, 131.4. 131.7(rC, AroEatic). I31.9(1C, Armrlic), l32s(3C, Arcmalic), 1352,
lrs.4, 138.2,I18.4(lC,AbD ic),1!90.''PNMR(300MH4CDClr,25'C):332.
2.8.2 lPdCl(2,9-din€thyl-l!l&phemDthroltne)(trlpb€DylPhospbitre)ltc-2u
PdcL(cErclD (0.25 s, 1.0 nnoll 2,9-dimth/Pn @lhFlitc (0 2 s' l 0
mol): Erphdylphoshirc (0.26 & 1.0 mol) FI-IA ([email protected], di): rO53(C 4AoDaric), 2920 (c-H, AliDh.lio), 2 847 (C-H, Al iph!ri.), I 590, I 5 53, | 492, 1449, raga,
rr39, 1095, 345,3ol, 699, 629,609, 515.,t49. rH-Nr'lR (61 100 MHz, cDclr,25qq:
l.22G,3H,r1r- PncMntlsUr.)t t44 G, ]H,,|,/aPh@n), ? l6 (! 3II, Ar lt,.t-12112"
phosphine), 7.20 (\ 6H, .|t-H*., ,/# -7.2H4 Pho6lhin ), 161 (d, 611, Ar'Ed
Jo'70H2. Phosphrner, 7 7!.7 81 (n, 2H, H' ' Ph.dnthrolmt 8O) rd lH. H' J-
s 3H4 Pnemnd'rolin.), 3.14 (d, IH, H1J- 8,3tlz, Phddnlllolii.J, 3 22 (d, lq, H" J=
s rHa Pherald&linc), 8 36 (d, lH, I{ -ts 8,2H?, r'llainlhbliD4 ''c_r'\rR (6: 7s
MEz CDCrr, 25oC): 27.4 0C, C,.CHJ , M.-Phcnlnthblin ), 283 (rC, g Me'
Ph€nqnthDlinc), 123.9 (6C, Abnalic), I 25.8 (3C, Aronltic), I25 8,121 |, 127 2, t28 5
(lc. Abn.tic), r28.? (6c, Aorunc), 128.9, Ir4 6, 134 9, 117.2, 118.5, 140.6. 140.7,
142.2, 143 i. rrP NMR (6: Joo Mltz, cDclr, 25qc): 21.28, Yi.ld: 71% o p 27l 'c
2.8.3 tPdCl:(2,9 dimethyl-l,lGpnen.nthrollm)(.risd-tolvlPhorP[lbe)llc-221
IdO.(CHTCN), {025 s, IO ndol)i 2'9-di6.thvlphad$rcliE (02 g, l0rml); Eiem-iolytpb6"nirc (03 g: l.O mhol) FT-IR (?owd.r' chr):3052{c-H
[email protected], 292 (C-ll, Aripbalio, 2849(C-H, AriPh.tic), 1s92, 1551, 1419' 14t4. rtltlro2, 85r, 7?6, ?49, 690, 563, 515, 481,4s4,
jH-NMR (6: 300 MHa CDCIr' 2s'C):
2.35 G, 9H, nr'r-phoElhine ), 2.98 G, 3H, M€_ Phmlhrline)' 3 49 (3' 3H, 'ir'ePhemninrclin ), 7.0-7 4 (tL l2H,,4Frl PhosDhiDc), ?63 (d, lll' If, J- 83llz,
PntrnI 7.?2-8.0 (n, 3I! Ed'?, rrt*n), g.tZ(a, rH' f,./= a:Hz, lhdlDthbli*),
s.2s (d, l}l, Iy',.ts 33rL , Pnemtuolim).irc N]"lR (6: 75 MHz, cr)cb 25€): 21 6
(JC, C, ,,rFpho5phiE). 2!.r llc, c' ,r&_PlEurt!Dti".t. 291 ll. i M?
PheEnrhblift), l2!.t, r2s.0, 125-5, 12t,8, 1269, 1276 (3C, A6rlic) 127.t (3C,
Arcnstic). 129.6 (3C, ^6dti.),
l3o.o, 131.4(3C, Arwatic), lrl T{!C' Abm.tio),
r!1.9,1322,175.1,137 2,131A, 137.S (3C, Aosllic), r39 O rrP NMR (0: 100 MHa
CDCI! 25'C): 24.0, Yicld 3l%. M.p. 247 "C
2.9.4 lPdclr(2,9-d1reft yl-l,lGPb.nrtrtbronmxttu-FtolvlPho.pbln.)lIC-231
PdC[(CH]C]9r {0.25 !, LO nool)r 2,9-dinEdvlpl*mrtelin. (02 g' l0nnol): rrilp-lolyhlbspnh. (0.3 & Lo nnol). FTJR (Pwd.r' cnr} 3OI8(C_H,
Aomriic), 291(C.H, liDhric), 2852(C-H, AIiPh.dc), lst5, 1557 1497 1'143, l3t5
I188, 1093,848, 804. ?09,632.610. 5lO,4!t. rH NMR (6: 300 MHa CDCIr' 2sqc):
2.17 (s, 9H, Mapho$hie ), 3.23 G, 3ri, ]t/a Ph.@), !.46(3, 3H' l'r.Ph.t.t), ?,21 (d'
69,,rF r/f,-7.!lta Plbqrhi@),1.@ (d,6H, AvE \Jt-7'Ht" Pho6tbitc) 771'
?.82 (n, 2H, H"', Ph.mdrtiE), 8O(d, Ul, g', J= 8-3H2, t'l*$.tFlin.), 8 12 (d,
IH, #. F s.31iz, rntuololiE), 8.21 (d, ltt, tf, F 8.3H2, lh.fu$Dlirc), 8 38 (d'
r H. ry', "/r 8.2Hr Pha$$blie). ''c Mra (6, ?5 l"oia cf,€b, 25'c): 21.6 (3c, C 'cHr, Phosrfiim),27.39 (rC. d,.CHJ. M+Phdrlhbli*),23'{ (lc. c Me
PhcM||rFlin.), 124.? (6C), f2J.1 l1C),1267, rt69.l21 tA, r286 (lC, am.lic)'
127.7(6C.Ar tic), 129.0,t14,?, 134.9,ll?.16, ll84, l4o5, 140?, 1421. 1437 "P
NMR (6: IOO MHa CDClr, 25t). 2l .6. Yi.ld ?t%. M.p. 270t
2.8.5 lPdcld2,9-dln.thylr,lGph.DtttbrclilcxDiPh.Dyl-2_Pvridvl-plGphh.)l tc-24 |
PdCh(CH!CN! (0.25 & l.O frnol): 2,9diD.6vlphcothloli* (02 8 l-O
nml); diplEryl.2.tyridylPIFcPlirc (0.26 !i I O Enol)- FI-IR (Po*d.r' cn r): 3O5l (G
H, Am{ic), 292qC.H, Alithric), 2348(C.X, Alipldic), 1596, 1552, l49r' 145!
1392, 95 (C-N), 1090, 858, 8la, ?Ot, 635,613, 510,451 'H NM (61 30O MrL,
CDCI' 25r} l.!3 (!, 3h, rvaPtaodmliE), 1 '18
(r 3H, ]l1aPhcontrli*)' ? l _8'r
(a 2OU, Prlu ftliE & irlolphirc} rtc IIMR {6: 75 MItz' CDCI'' 25!C): 27 3 (lC'
C,{H! , rl/aPhautbolim} 28.3 0C, C rtaPn Ndmli*)' 124 5 124 8 (1c)'
r 25.1. | 25.7 (2C), 125,8 (4C), | 2e.4, 126.5,126.9,171.1,127 2 r2A l QCI t2E 2, l79 l'114,7, 134.9, l3?.t6, !t8.4, r40.5, l40.?, l,ll.l, l4l,l9,rrP NMR(6rl()0 MHz. CDCIr'
25.C): 21.7. Yi.ld 80,6. M. D. 261 'C.
48
2.3.6 lPdClr(2,9-dinethfl -r''0-ph€rrntbrulinextricvclohexvlPhos-phir€)l lc-2sl
PdCldCHrCNh (o-25 & LO mol); 2'9iitulhvlphtuinditu (02 & l0nnol); ticy.lohd9pnosphi@ (0 28 8; I o nDol) Ft_tR (Powdd, cdr): 1054 (C_H,
affiaiic), 2922 (C-H, AliphltD, 2846 (C_H, Aliph.tic) r 593, 155?, 1497, l4r9' r3?3,
1195, 49, tOO1, 849, 733, ?21, 652. 610, 5lO, 489,440 'H_NMR (6 300 MHz,
cDCl:,25'C): 1.28 (m,33Il, lricyclokxylphotpnilc ),7.48'7.57 {m' 2t{, H'',Pneemhrclift), 7,81 id, lH,Il,.F 8.3ll2, Phdrnlhrolire),8 ol (d' lH' I/. F 8 3H2,
Ph.nen).81? (d, lH, lt', F 8.3H2, Phd.ntlmlirc), 8 ll {d, lH, 1L F 84H1
pheEdlfttina).rrc-NMR (6: 75 MH2, cltcli, 25'c): 2?5 0c, C,€H! t/.Pr.@omlie), 2s.r ( t c, c', ,/ePt dntbFlie), 2?.6 (6C) 27.9 (3C)' ll.3 (3C)' 32.0
(6C) (ricyclohcxylthoryline), 125.9, 126.5, 1278, 123 ?, r239, I292'1t11, r!16.
133.4, 140.5, r42.r, 144,1. :r? NMR (6: IOO MHa CDCIj' 25'C): 249. Yicld 32%
M.p.217'C
2.9 PyrlmidioeBenzrmide Ligrnd$
s.hd. 2,7: Synlhsi! of Sut6titu&d Prrinldim-b€l:did. Conlornds
2.9.1 Sylttgb of 2{hlorN<pydnldt!c-2_vl) b.Dzrbtdc ILrlTo pynnidin. (0.a7 s; 5 nnol in lohl ErtO), Plrid;E (0 42 tL 5 MoD s3
..ld.d !r Ot. Ih. €cti@ nnM we ltiftd tor 30 mir 2{bl@bdevlchldidc (0 87
s; 5 riol) qd oddcn dbtwie Gultins in ! n$id solution. rh. asliftd ar roon renpfdturc ovdigh. Th. puF podtrcr wa .x$!ct d with cHclr (78%
yi.ld). Mp 137C. Aml Crlcd. c: 56.54, Hr 3 45, N, t? 93 Foud: Ci 55 99 H: 4.01'
N: r7 s3. 'H NMR: (6: sOOMHz DMSOn6): 8.Os (N'H);8 94-8.96 Oc of-NrcrHti
6.92-6.96 (Hc-N,Cdlt ; 7.?q?.8r CIf (Cl-C.}|l); 7.55-7.56 CH' lcta!l'|)t 1.a2-7 41
cril (clcdHri 8 60-8.6 r cHt (crt6r!) rc-NMR (6: looMH4 DMsonOi 1672(c
'o)i 157.? (C-l.IH)i 146,0 (c1; 142.7 (C)r 131.0 (c1 132.0-112a (c')i t271)27 6
(cr)ilt0.4(cr)
2.9.2 Sytrtbeiisof 2-m.thyl-N{pydnidire2-yl) beMErdc [L2lTo pldnidinc (0 4? & 5 nnd 30dL El:O) pFdirc (0 4! oL 5 nmol) sls
addcd 6l o'!C. lne ft&tiot oirtu€ *a! sdrtd id 30 nin 2_D.$vlt€nrcvlchlorid.
(0,?7 !r s nholl ws cdd.d dlotwie suldry iD . torbid solutiot m. Ection E xluE
wls 3riftd ri M l.nF.tuE ovehish! Th. plE Podud was .xl!.ci.d will cHclr
(72% yi.ld). Mp, t?5t. Ad. c.1., c: 56.J4 , H: 1.45 , N: I?.t3 Found: C,57.03, H:
2.98, N: l?.6r. 'H,NMR| (6,IO0MH4 DMSO-d6) S.05 (N-H)i 8.59-8.60 lH'X:CrHti
7.27-7.34 (!r N,C.Hrr 870-8.71 (l{-M.-C!Hi);7.86-7.81 (H1M.-C6Htr 743_?.43
(11-M.-C.rL)t 7.so-?.t1 (grM.-C.H.); 4.31 (CHt. 'C-NMR (61 300MHzi DMSO_
d6)r 168.2 e; 1a6.2 C9;142 ? gi ll95 C; lt25 C; l3l9-1t22 q; 1309-l3l0Cli
130.2'110.7 C;127.6Ci l26.1126.aCi 215 CH:.
2.9.3 Sytrtbgis of 4{bloro-N-(pyrinldin$}yl)belt.mtd€ [L-31
Plriridin. (0.47 s 5 mnol)r4 chlob.nilinc i0 37 s;5 mhol) Ihe purc produci
*.3 .xr&ted witn cHclr wirh ?4% yi.ld. n, p., 164'c ADtl crl,cr47sl H:290'
N: l5.ll .Fou.d: c: a6.9, tl 322, N: 15.5r. Ltt-lD"[a (5: 3@MrL: DMSon5: 3 04
(N-H);3.s3-3.56H';6.8?-6.rlrr:7.50-7.s41{11.9n-194rr' 'C_NMR (t: rooMHa
DMSO-d5r 171.6 C{i t66.1 C-Nr 1626-162.4 Cr 150.5 Ci 143.0 C; 1363 qi
1r4 6-114 3 Csi 131.8 C
2.9.4 SyDtbesisof 2-bremo-N{Pyrimidtn.-2-yl)b.Dantd. IL_41
Pyriridin. {0.4? gi 5 @I): 2-b@drilin (l 09 s; 5 nmol) The pm podu.t
w.s cxdctd vid: CHCIr (84% icld) M.9., .154'C Anal. Cal., C: 6? 59 , U: 5 20 ' N:
19.71 .Fourd c:68.0?,H: s.59,N:20 13. |H-NMR
{6: 3ooMHzi DMso-d5 8 07 N'Hi
s 96-8.98 Hi NrqHt 7.23 H(-NrC4H4 ?.7?-?.78 Hd-Cl-qH1i ? 44-7 50 *t 7 61'176
50
H4 8.66-8.68 Ht. 'tC-r${R (t, IOOMH4 DMSOjI: 16?.8 r; '58.8
C; 1465 C';
r42.4 ii r3ai Ci l3l.oC; r31.oCr r28.2 C r20,4 c,'.
2.9.5 Synthe!is ot4-methoxy-N-(pyrlmidine-2-yl) beDz.mid. lL-51
P)rimidin. (0.47 si 5 nmol); 4-n.nhdydilin. (0.85 e; 5 mmol). Tnc plcproducr wrs dr@ted virh cHcL (?89/. yid't) M p , 162'c .Asl. c!1., c: 62 87, H
4.84, N: t3.3t .Fowd: C:62.41, H:5.33, N: 17.8?, rtt-NMR: (5: 300MIl4 DMSOn')
8.07 N-Hr s.99-s.96 lfj s.7+s.76 rfi 6.97-6.98 H'j 8 5O-8.5s 11; 3.e2 I1 t-NMR
(6: tooMH4 DMSH} 16?.5 C4; 15E.8 c: 157.6 c; 16l.r C; l lo.a C; 127.7 c;114.3-ll4.8C: r3t 8 r30.8 C.
Trblc 2,1: t$clcd stutuft of Botuido ConDoundr
Model compoutr&||-NMR) Mod.l Cohpoun& (!C-NMR)
210.t I"arFI-EFN,eF*g
7_t0.2 ,Z'lsp3
210.1 fF*g210,4
.". "n e"e \cl-E
210.5.|-,". i, s ,4\qB
5l
2.10 Copolym€rizetion of Ethylene with Polar Co_monomers(Allyl Ethyl Ether end Allyl Bromide)ralkdiun (lO) tnd br!.-n* pllladiun (P^O) clElysll *d mplolcd 10 studv
rhe copolyndizrion ofctbyld. with difi.Ml pollr co-nonon.s lit allyl ehyl dnd
a.d allyl broEide dnd rh.ir ihcogontion was invcsliaal.d alorg *nh th. nolecuhr
qcigh of lne copolJm.s by difcrml NMR .xp4incnlt Tno nol.culsr wcighls of rhc
copollm.N and lnc incoltoration of $c polrr cdnonon.s i o niin blckboDe or
polyedrylene *a6 cmpa€d
2.10.1 syrrleh of (P, o-M€o)Pd(Py)Me Complex€r
' !"i",(
scL.n. 2'3: Synn*i! ol (PGOMO Pd (Mo) !, d6lvs
A $lDlioD of (IMEDA) PdMc, (in 6c5), (PO, OM.) H ud Dtaiditu in nsws dimd for lh r 30t. Th. nttoE obhitcn ws wisncd wirh di.rhvl .thct 10
emE !yp@du6. Th. t€Uow F.ducr w$ !g.in tlrid.d by dislving n in cH:O,
rnd pEipiutins it vith di.rlyl crha ed dryils i1 uldd v&u!n 'H-NMR $eh *sobbi*d for comp.n$n *ilh pEvious csulr. lrl.
2.10.2 SyDtb€sb of (P,O-OMe)H Llg.nd
/>N,so l.
rY'
o
(6il-u -""* (dil,:.
Sch.D. 2.t: Synrhsn of! (PO.OMo)H conpoud
(Ri.s.r's ps.dutc !r)
^43
FrPP^',r.,W"vo".. \-/ \- -M. -
.r."n"- 11
S.b.D€2
2.10.3 SrothAii of(P. O-M.O) b$€-frec Pd CoDPleret
A solutio. of [PooMc]rdey)M. (0.6s: 0.9 mol) in dri.d CHtCIt (lonl-) was
c6l.d b -73oC .nd ! slulior of B(C.Frh (0.158 ; 0.97nnol) i! CBrCh ()onl-) wsld.ted slryly. Th. iir@ *s.rb$d to wm io @ En!.r.tot.Th. eltar ms
rcmorcd udd v&uuD od 6e;sidu. vt6 w$ned wilh be@*. h.xrrc sd dned
2.ll Characterlzrtion of poly€thylene .nd co-polymerg
All chrcDiun cmplexes qc.Dl 2,tuinuoGN-(116{q!indlin-3_yl)€$yl-
idflc)b€[email protected]! (C5) Foduc.d lilnifE$r quftiiiB orpolynG Thc polyndobbin n *E chmtnz.d by IR sins Xlr di$ tt rh. Engc of aOO(H0O cm r' Th*Dolyn s !E linor .onfmcd by ch@Hilric lb$rDdd brnds of C - C hd C-ll.
Diffdmtial Scamins cdorim.try (DSC) lmlysis of .ll polF.ts tra elscondul€d on a P*kin-Elnd DSC @lorincld which illuttald lhll thc nclting point
6ng. is l2?oc b l35oc wi6 aagi6 b.N*i llclT? Jg . Tho Erction t nDqa@
h6 als . sut irLt!@. on Tn rc) of PE. 'nE @tion hDaN i,c@ !l$d.c€.c Tn. flE* qles e @situr ,in $a r.lucs obtain d ld Hid densrq
poryahyrcrc HDPE ( l3). Dificdill Scanning Clbnn.iy (DSq m.Iing ouG @@rd.d d i nrc ol20 qcDi,ir. Thc ftlins cnD€EluE (I') vrhd rspottcd w€@
obbitud fton r4ond hanng curc.
PdeoOM.)M4Py) od bcs. fiB Pd(PO-OMe)Me cablt5b e.E u!.d for co'
polyrenation of.rhyl* eirh .nyl cthyl dna &n rlM bronid. Il)c copolvtn 6obhi..d w.c chlncErizd by ID .Dd 2D-NM& DSC lrd GPC, I0 cle of ID-NMR,
odombd urB 'n
orlonlim irlo Fly.dryl.rc v6 inBigacd by 'H_NMR. tNM& and dE$ NMR !$is:fuE 14 tuih.r oonfiftd by DEPrll5, cosY $dHMQC. thc ncltinS poirt! *e€ detcinin.d by DSC Tlt ircorpoEtion of rh. cG
/^.:"':\I / ol\"4""i+-zQ),*ac,,,,
5l
ndmd into $. Dolr.tiyl@ b.crbonc rd rchcdd wighls (V') ofpo'vnd md
coiolyrnd r* 6lc!hr.d by |H-NMR tpet!$opy. ,v, *6 .Ls d.t.finEd 6v Grc.
REFERENCES
L Ammso, w L F;Cl'd,C.L L Prniicrtio of lrbd'lotv CheDicdt , 56
Ed. ISBN: 0-750&75? l_3, Elscvia S.icE, 2003
2. Harlcy, A. K; Nowrolq L t :,N.gd,B. Orynanztollis. ,0o3 24,2155
l. Drerr, E.; vrn Drjk, R.; v.n Gin*.l, R; v.n Oon, B i ?ush R \' C'm cnflnut
4. Kdhi, ti Yosbino, K;l{oati, K Ddlor 7tus tO06, t 25
5. Arra, N. T,i Cood.ll, B. Li Mchlolh, ! H Er Pot lpPI 20{1,
EPt?60036.{2
6, S!, B.; Ztto,l.r Cui, Y; Lide, Y. ; Sun, w H Syd' Cott d 2005' 3 s 2317
? su., w H ; T!ng, )ai G.o, T ; w!,B;Zo&1l/;M! g J orad@tt
ch6. l0/'s, 690, l51O-
8. Sur,w H.;fi.o, P.i Li,G; a.ng. Si w.ng, w.l Yi Ji A6m', M;Tang N J.
Oryanohet. Chd 2007, 69 2, 4506
9 Aur. M; Adauli, s.; Krd& X i Brdshth, A; S!n, w H OrS chd L'tt
2008, t 296.
rO Amorqb., S. A iAn!,M; aun8, Mi Li,G; Su,', w g "16
J ClEn 200a'
Il, v.lr,J.;U.f,C Ri Sh.4 z,Jddtn'R t Orcanohe'a|ict 2001,26 6624-
r2. Luo, s.;vcl!,,; Li.f. C. R.itord.Ll F J rtuCh'd Sot 2oo7, t 29'8946
,5
IESULTS ANDuscuss/r)N
Cha?ter - 3
RTSULTS AN'D DISCUSSION
3.1 Chromlum Complex€s ContalDlng Substituted N-(l-(G(quinoxdln-3-yl) pyriditrF2-yl) ethylidene) benzeoamine
Hsc
Flgur. 3,1: Cr(Qrirdllmyl-iniDopyridine)Clr
[c-l] [c.2] lc-rl tc"4l lc-51 lc{l lcrlRI
R2 H H H H H H
All llr d.snbd st.ddimt d.hrmiuF (III) conplds, [C-ll ro [C.7] w@
strc€stully synrlE izd rnd ci.etaiz4 Thc @npLx6 e $.nb in $luim 6 vell
a in rb. solid shE .rd w@ i&naficd by Ft-lR dd clddbl Ntlb HN.rd, de
to the pamnlgrcric utlE of ckmi@, NMR sp@ti could tu. b. obLin.!. lldatllnalyes (C, H .nd N) w.E Frlmcd dd Stvc Sood r.snb
3.1.1 FT-IR AnrlysisFTIR speEa r.valed that lhc C-N slr.thing fiequenci.s in quimnlinyl-
iminop"idinc liglod, rtDer.d in rh. m8. of 164!_1655 co r, whilc oEe fEqu4i6.E shii.d b lovd {lrc (159215?3 fi') .tur @DI?r fomodon. The @ll5clarlv shov ! c@ldiDdon inrdcrioD ol ti&ntib sbstiol.d quinonlitrylintDc
ptddine ligands with th. nctal h&r.
3.1.2 Strgl. Crystrl X-Rry AndyshSinsl. crysiil X-dy diftlctid fra3uEd fd conpld [C_3] *.r caicd out s !
Brutd P4 di&rcM.6 with sE9ni. nonekomt d Mo (! r.di.ti6 (l = 0710
?l'A). Cc'l F-m.LE *@ obrlimd by Slobrl Ef|].ffir of dt tdidon of an
col4r.d Enedotu. tnc..idcs we .o@Ed. Thc shcie wls $lv.d bv . diEct
n.thod dd €fin.d by tuU-Eatn lnst sqsm o F2. Ar! H .lms *cF pllc.n in a
.rlcul.Gd positid SrructoE slulio .rld E6mmdr wR Ffod.d sins rh.
SHELXL-9? prck.8.- crylbl &d ftd pdBsirg p.m.t B .E sum.nzld ir Table
LI Clyslallornpbic dota ol oonpld [C-3] hrv. bm d@osirod wilhiD thc C.Db.idgc
CrylolloCnphic Dra Cdbr,
Fd X-Ey stuctnE clu.idtlio $ihbl. crysdls *ft 8rcM by slow difi8o! of
m.th.nol 'nb
r drhlom.th.nr $luron of tlE conpl.r thc -otsuhr cmcrun rshon i! nguc 3.2. TtE pyridin N(2!C(l) 2.004 (4) boDd did!@ is shotu rhin in
qdrcx.liryl Dit gm N(3lC(l) 2.128 {a). E@ tbc pyidit. N(2} Cdl ) 2.00{4) bdd
disr,tu. is siorc. fio rhc inino N (l> C(l ) bdd 2.16l (4), Thc bond sdc of N(2)-
C(l)-N(3) is 7749dwnil. N(2)4(l)'N(l) i, ?6.33 A. How.vd, bond.ndc ofN(l)_
C(llNO) n 1s4.30 L All rdu.s 6n6m i diston d @bh.nd scm.ty of 0E
cdrplcx. Tt'. bond ldglhs of C{l}O(2) Dd C(l)"c(3) e 2.2903 A rnd 2.2929 A.
Th.y .E shond lhan lne C(l).Cl(4) bmd Imgth 2.3299 A. Th€ conpld cxlibi$ rdisbtud oshcddl EEom.q, du. b or bulky quhoMure.idim I's|nd.rrl
Trbr. r.r: G)6rllosFDhjc d.h oftlE cramDlcr [C.]l
b (A)
8O1o.v(A')zD c..d lBcmr,Ab$Dbon @incimr./ (mm )F(000)
R (7.)Rw (%)
s82.88
8.2134(2)33,360r00)r0,6156(3)
95.57!12)
2907.,4,{14)
1.3320.69512041.22 -23.3028941
006150.13740,871
ngu. 3.2: 2, 6D.tbyl-N{l{6{quiurlin-3,y1)Drridira2-yl).rhylidd.}bozfunirc.C€L [c_2]
J.2 formrtion of acetylpyridine from 2,6-
dicarbdboxnyridine
Thc sl. ofbis(iDino)pyridine od noDo(inino)pyridirc d*ivdivcs cs tislnd! iicompldes oul aE us.d for €dyric .dryl€oe Dol)ftliatid en nor b€ or.t.nphasizd. Folloyins lhc ind.FEndc di$ov..y or 2, 6 bn(imiDohridrt ncrd G.and Co) @mpLx.!, F sucn €bvsts by Br@knrn and ciblon opcncd Lt. dor ro hiBh
d.Niiy po\€thylcnc or llplE olcnns. l,{. M@ovs, rft6 rh. piolM wo* orajiimiDoni.k l 6npls.s s aLlysl! ld dlyto* pobndizlrion 0, idji6p"idir. nicr(.r
conplcres lrqrrrind $.i' dibdic.nlogu6 I'ir werc folnd b b. lctiv. c6t tFs fo!.ihyloe polyn.dation. Worlh to be maliorcd dE prDladon ofth.e inino-pyndin.
risrDd! omoDly inrclv.s rhc us of @qt. or fomy! plridin .s snirg nlt ri.r. To.lploE the alr.n.rive nod.k of laL-r.nsition n.6l cfrplqe a5 rh. @lalysrs to!crhylde p.lyncriation lr: rl 2{nb.dDxy-6-i€tytprridin (5) w$ tusl pEDlrcd
thbugh ill. cmdouabL Fefomtid of Don€arb.rytAt jrlo an letyt golD with
th. subtue of dicarb.rhoxyptridim (t) qnich cmndly rsfoms inlo 2. 6-
diao.lylprridinc (9) lra rr. Tnc n.wly obt in.d 2{arb.rhoxy-6-accrylpridii. (s) w&found ro b. an ioDori.rt cbcmi€t fo. !y h.siing sm. albunvc rcw dgrniccoDpounds. For.rnplc, 2-quimEiilyl,reqlp,ridiic ws prepotrd and u.d ro tomm.6l coDllcx.s !s cahlrsls lor eriyta. polydciz.rid lrtr4 How.v.r, tie modly
encou .rd pFbld i! pep&jn8 2rdb€rhory-6{@!,lprndirc (5) is thc rom io! or
by-podlcl dletylpFdi* in trDdos Fodifi.d FaeduB lr' r'r ud n is dimcuh bhaituir 0E hish *lativity in d.ry lomiDs 2<eb€rhdy-6tc.lylpyndD. (O wirhod
obedins dilc.lylpyndin. (9) {r'1. T}dcfoE, it vould bc t.o.$qry 10 undqlr!.d rhe
dciion ncch.tusn, and find ln. optinun cmdinos &d gddl pl@dlt fd lmingde lc.tyl gFup froE ctrh.thoxy group.
In l]l. pr.vious proc.dlElr1r'1, 2{rb.rhoxy'6-eetylpyridire (s) ws fon d i.the reclion ol2. 6-diorb.ihory pttidin 0) wifi EtoAc in th. pltmr ol vanous
anon ! of EONa. Dlc lo th. mistuE @i.iviiy of rloN!. d. ruipuLtio LolDiqu
and r.crio, @ndnion 6ily .fiacd il! yicld Dd byrodlcr. Dlring rh. tulforud@oi th. *lboryl.c i o D lc.tyl srcup, rh. r.chanisn ws .rplri!.d 6 Cl.i$n .ddcordcnsltion b fom !-k to ..t!s []91 Ino followins slcp wls prcposed s tunhd
hy{kos.nn'on b pdtu@ . p-lclo &i4 rhich *s nor stlblc a.d ws d@npolc<t !o &aEryl gnp. sh, r4l orbo dionda rr'r. HN.€, rb.E ir m rpon *hicn d.:entcs
rh€ i$l.rion ofta i .mdi.r6 I! thL work sodiM wiLvwitnod [email protected] of e$rml in rohcnc is b.d ulcd irsG.d of EoN!, hd solely oDc Drodlct
eilhd $c none d di&aryl slbstibten pyridind oould b. obbinn. h addiiion, lhe
'ni.m.diat of tne Ft b *c6 *€E individ.tly i$lard..d iMrEr brMll @utd
p!€duc. rh. tidc onpouDdr !l.pwis. Thle inEm.di.rcs urd p:qbcrs pbvi& 6rsr,
hand .vid.nc€s for uDd.Br.ndins then phusiblc raction h.chlni!tu. Ii.ft, rh. dcLiil
ftsulrs lre r.pon d alo.g with dE di$u$jon of tljc pltusibl. hah.nisn.
In dE f@tior of 6{c.iyl2ert dFrrlyidirc (t lrd z,tui.arytpFjdiic(9) noD 2, 6-{tic.tb.thoxyptridirc (t), n i. cld thr rh. Chis 6ter corddsltionbkc! pltoo fmins th. coftsp.Ddins rn.loSrca of 9-Lelo csrd I,01. Then th. foltowirs
hydolysiB in acidic rqu6B slutio will hTp.D ed cl.rv. th. u.b€rhoxy group wirh
thc n@6ity of eicErd F:.rion r.np.EoE. IrE inpodnr ise Ellrad b th.cdr4ion ,icld vill invols rhc.treii!. foturior ofdicrhoxy{ropopdol.r. (2 or6), rhich th.r p1bducs rh. Fkclo esr.r lDioDs (3 or 7) nEle sggolcd lnioDic
conDounds corld nor b. diEdy obEincd at fiis momflt fiow.vd,ln. i.ohbd p-t.io
e..! cohportuls (4 or 8) 6uld Plovc ln. pED@ of Frdo .!o.r si@ (3 ot , 'r
rh.
b4n $lution. Tb. Ft io 6h @DouftI! (a or 8) ieht d 6!ld rbvi'b dnerelid.nccs i. fonirg ao.ryhhc conpouds.
59
tn dr. c{ book of orgsic cbmisq, n is cmmon b sho* dut 6. fo'mrion
of an acetyl ssup Ird . p-t.b .*s con occur in 5 hydolvzing irs 6t r grouD lo fom
rhc 0 kcrd rid m an intemcdittc i1 vd t hy?orh.sis [email protected] in a prdious publication
l''1. rolro*i4 thn phio$lhy, rcs.tdiDg ro edvl 2{lrb€thoxvqtsk b_
.arborylaE)Dddin (O as rn iimRnirE, iE hydol'6i3 could ha* No posibilities
d!. ro No.st r groups wirh linilar chdicll .nvtom.nt, rnd lh€ 6_ac.tvlpltidine-2
crboxylic rcid vould h. one by-pldlct It facq 2srbelhoiy_6{tsk co.bqyhc)Drridirc (,t) cldifas rh. [email protected] of rr. fomltjoD of.@iyl cmDolt(|s
fron Fk to .st r Mlosu.!, in which lhc .l.tvas. of ! ciftoxyla& gbuP t mot
ln . 6!rin., rynoEtic pe.d!€ fomin8 D H.tt6nior dborylic 46. ibc
&diun .rhanod. *3 connonry p.Aed . d.icd ton il! admol soluli6. Hwwd,some elbinol could rcmain in thl solid NaOEt, .ven *hcr il t6 dned und41,cNm
line Mo@v.', $diun hydbxide @uld .l$ bc .n inpuriry conpolnd du. to ih. linle
lmur ot v.t r lminils i! 4bmol u$n. IE* fictoE viu lfat tt sl hou't 6r
NaOEt, lh.EfoE il is na${y ro uc an dc.siv. dNr of NroB rr': L I I e} lor the
rdnsfomrtion elctiotr. Ll6.iD, irstad oi ugins NaOE! tnc sloicnion.Eic e!.dor of
clhml ud $du itr lolu.na Dovidd fi6h N.OEI in cf-riv.ly actiutin3 d. Cl.is.dd cdddsiion. wid' thc $n; volk-up prcc.ss, botn deiEd pbducr!, 6{evl-2-carbefioxrTyndinc (s) md 2, 6-diacdyl'D{idi,. (9), wd oblajned wnh hislly
inproved iclds. The 2-s6.doxy-6-accrylprridir. {s) could b. Flp.Ed in 6l%
ielaEd yi.k wnh m .quisldt of sodiM Ed.rb.sl itubd of45 % tidd {rrl.
M.m*hiL, 2.6ni&.tylp"idiE (9) b ,.Daed in 66.1% yi.ld wirh 1.0 .quivaldls
of ediun dd ctheol conplr.d with rh. ln*atu€ yicld of 58.8% rrr, Bcyond r.b! lnis
preeduE nede l.$ oolnts of subsbnc.s l.$ iib. and .n.8/ In lhc rbchion.ticlmunt of sodtun, .rhlrol .nd 2, [email protected] 0), a tuc of 2, 6niie9lpridin. (9) was obsefl.d iD .dditior lo 2{.tb.rhoxy-6nc.tylp}ddin (t r.ct to tne
fomaiio! of @dbhion ccrboxylic 6Lr. lhc n$ction of NIOEI is ro Enov. hydride
nm erhyl r@dq th. sodilr @uid b. eF.-red io lloaly Fodu@ dr|llado!crnoxylic .!tr. adrdirgly, ria hisl cormhr.d .thyl rc.rlr. slurio wi6 sodium
will diedt produc€ son. B-k.to .rGr. To rloid c$lnol foft.d in th. r*ciion, .hc
toluene b u&d !s solvcDl *ith sood solubilitr ol2, 6nic.$.lhox)"yridift (l) ddpodlcll. with firilg domr 5 .quivdolr of .oryl {d.e b 2,&icar!.thd}?ridiF,
rh. roft.tion of Gac.tl-2{.d€$oxrTyridinc (t or 2,6ni.@tylpFdif,. (9) was
irdividully imprcv.d thelgh co .ollins rh. rnomis of sdim. Th. 2+!Ibcrhoty-6-
.€rylplidin. wis elely [email protected] in 67.1% isolaLd yi.ld with onc .quivalht oisodiln, qhrl. 2,5-dietylDyndine 6 i$lltcd rs rh. dly Droducr iI 7l .0% yicld wih
Unnl now, thc anouft of difieEht r.aclanE h!v. bcdr tully ddsideEd lor
fomadd 6-acciyl'2{srb.rtorr?yndie (5) or 2,6-dnetylprridinc (9). Th.Ef@,
Efrio n€hDtm shdld h. Evis.d .s d*db€d !bov.:
ln lh. r@tions ro fon rwo peducts 5 dd 9, the Dsr.bt. dietnoxy-
oxopopanol!1. (2 or o aDd p.t 10 6Gt dio6 (! or t) would be in&m.dirt s. Ethyl
.c.rir. @cb wnh sodiui lo fh ! 6'brio, cfborylic 6Lr, whiD old n pwi&
Ead wnh tuo c.rbelhoxy 8rcups ot 2, 6-dic.rnclhoxwyndinc (r). Th. pEenc. ofN!OEt could som.how Esult in rn unbiluccd Eoclion lo fom nixrr8 ofNo DFduct!virh 2, tuicrrbdtb4/p,"idim (r) !€rui.iDs. Hovdar, lodid i! nor dn&lwd itloludn Md rcact5 st gwie wnn 2,tuidrb.lhoopridi@ O) in rwo 5Ea.r d thc ba*or th. sodiDn lbounls. Ndnaliaion wnh diluhd HCI in ic./watcr blth i.pEs6, ih.
'ntrnedi{cs of Fkcb @boxyl.E 4 ad 5 wE idrividuly ep€sred jn
8ood yiet<ls Ileb in sffil .*cprcd tur rh. tydn!6i. of F+c!o d$.ryt&s sivci dE Fr.6c0borylic rids lr'r. Howaa, $d. is rc Fle oi 6-rc.rylpridiE.2{uboxyfic lcidobetudd in tlE hydrolysb of p-k ro olt6dylat s 4. SiDihrlt rheE ic ro rnitogucs
bc.n4 @boxrlic .cid i$I.t d in fomi.g dj.@rylpFjdirc (9) d'od rlc hydorysi. otdndyl 2,6-bis(F tdce$o:yhE)t'yddjm (8). rn addino", it ws repod.d rh,r lhc Fk.ro carboxylic acid was sbbl. erl. Tt Efore, n would b. bene! corljdenre an
.lcn.livc nahsisb. lnsta4 rhe ctav.g. rerj@ ot . Ft ro .sr rDtir.r thc a*rylSrdp .nd .thyl c.inoxyl{c, vhjcl t s un$bt. int mcdirE d,.t a b. ddilyd.conpoed inb.rh,nol md crt'oor djoxid. Ihh ph.n@cnon q.s also ob.cs.d in th.syrthdis oi l-chloD-2-.tkinon6 l,:1. Tno distty d@mpoling p-kelo o.rboxyric.srdiMmcly anti{lis! !@id, will poecd in tfic pEenc of pbiG ro gjv. e [email protected]
Stoup rnd.tlyt.dn ryl.rc. Iu)
3.3 Pall.dium Cohpleres Co
f, _,("."{ )f-I
lL11
Figur. 3.3: Prllidiun
ntrinitrg Mired Donor
lq' fn ^*lPfPdtNlU) |
tct | _:- |t-
lt2)
Lig.trds
All sFd.sizd prlladiun cospld.! EE chrncEnzed by NMR, IR !cl.n nbl odyeir !.d singlc cryst l X-ny Mlyris, The E$l!s confim.d th€
@rdintio. of N- a.d P- @ntiinins nt.n donor tisand! io rh€ o.r.l hlrq t1E
clcoerhl auly*s {C, H, \t srrc sdsryi!! Nlls I* eldDs poinls rE in rh€ tugc
3.3.1 SD.ctrc$optc Ctncierialior
3.3.t.1 FT-IR AlalyrisThc iniia-Ed rpe$a ofconpl.x.s IC-81to lc-l9l Gac Schctr r) s. cmistent
wnh Ure mol4ulrr rhc@r rho*ing.tt buds Equrld lor tlE cordDdon ot |l8lnde
ro $. p.lLdiM c.nier. All cobtlc"s dnibil Pd-N and P.t-P lberprid bxxb withn!
lhc En3c which confim dE c@rdiDtior of $. $bsrirui.d .nitjre dd phosDhinc to thc
Pd (lD neLl 6td. Ihc vdua e comlanbL ro dE liLr!tuE v!lu.! rza), scl.cted rR
tb.ri@l rl!6 @ lisrd in rh..xFrinatrl sdd.L cmpl.x c-9, Pd (dicyctohqytahjrcXlris,piolylphospbjn )Cl:, rhc qnbc.
oi an N-H vibntim of dictlloh.xyldioo indioircd by a D.!k at 334? cDr In $e fre.PhrP noiely, . si8ni d l4?4 cD"r@|!gls . P-C vibntid shict iplar.d wid . rdshin .t 1465 cD-r .ft.r conpLndon @ffhjI8 dE ditiDlim of lhr! with pd 0I)n.bl. A band !l 16s7 coL Epr.$nr! thc vibstior ofphdyl gb!p5. Illc lbsoarioD
bmd! for Pd-Cl e h lhc nn8. of 30G332 cmn_ All !b&rpti@ vituca h.r. b.cn
r$i8r€d &@dinE to th. IiEntu Prr.
62
3.1.1.2 NMR-AnalyrisTh. rH-f,'l,,lR dr. (in CDCIr) for .mplcrs C-a ro Cl9 iddrifi.d lll prorors
by $.n inasity and muuiplicity pan.d dd rh. bbl numbs of potons was olcul.tcd
i. a8Fcn widi th. cxpal.d Dolecule stuctuEs. Th. ry.chl Esllls Eve.lod th.t
$a k r .tnifiot domfi.ld shiii i. dr.orplcxrs ir @npuisD b ln€ ttc ligdds
which cdtutu rhc [email protected] of thc ligrn& lirh D.d 6r.6. Th. dEPhrP noiery shows r nrlritl.t sigral ar 7,34 ppo Frwhich rfid mrdinrtion with
Pd(Il) cpp.5s in tne nngc of 7.3 8-7,?2 ppm h lccorda.dc lo rcponcd valu.s l:r:6r.
ft. mmtic poton siguls of lolylpno$nine rsorrD6 in the msc of 6 =
7.ll-?61 ppn aDd tlE 6 = 2.?8 ppn '!s.ne is orlrib{t d t. d. CHr noi.ry olrolylphospninc in th. c@9lcx6, TrE mrdi. prorc ol sbditut d dlir. aOp..r itfic nngo of6.9?-7.23 ppn whici iils wcll wiih litdtorc !alu*lal. In ln. cmplcxcs C-
8, Pd (dicyclohdylanincxLi$r-tolylphosthin.)Clr and Cll Pd(N,melhyhnilin.Xnie
pbtlph6phine)C1,, dE CHr noEq of sutcnod eitircs tetuB ar 3 08 .!d 5.J I
The ic-N}m di!. cl.dly rt$lv.! lll c.rbd alons pElcm jn 1ne oomFounds
C-8 ro C-19. Tlrc 6MEr of Dhcghjn. .Dd eiiE rE lhind do'!6old in d..mplcx.s s compaFn b rhe lE ti$n<,r Thc arbon .lms in ihc ii&tiph.ryhhosphin. lig-d E;E ar 6 -t 28.4. 128.5, 133.6 .rd I34.2 ppn Es!-riv.tyPt ttr lnd ifEr oonpldrlid in lnc 68c 6 - l2?-l35ppn, Th. upfi.ld shitod C {-p)Eson.ncc in the Phf moicty is artribuicd ro I shift ot el@trDn d.mit nm tnc nc&l
'on io*tdr C (-P) dlc to th. r{c.€ptiDa DiE ofrbrt.
Amric C tlo anbotu or $htrituid anitinc Isnuc in d'c n.g. ot o - 126
129 lnd 135.05 ppn. In dE cooplq C-3, rh. cyctohdyl goup is .teron-do{tinA.'Inis would incEo* ihc dou6l. bond chldcrd of the C-N bond lDon cooidination
calsin8 a dehjeldhs of qrnoD atom !$chcd !o d. !cr.l cmt r. nE cdoB otcxroh.xylbic slDv ri8rL i, th€ nn8. a - 25-56 ppE. Th. mmdc c.tto6 in
lolylphoslhir. Esomt ir th. mgc 6 = 141132 ppn $ @nprcn b tne fe li8{dulu. 138-129 ppn l':x
':rl .Tlc C'lr- bojctb! of N-nelhyl.nilirc .nd tolylpho9hir.appqralS = 24.? rd 2l.5 ppn, ho*evcr, iD $. na IS.nd rh.y !pp@ !t o - lO.2 dd
6l
'tt pEm@ of thoc sollm.r clsily ndif6t d ln. @rdin.tid of hotr
bsli$fd inilino snd pholphine lisandE !ho!8l N- dd P- to lhe bclal 6nler' TlE
.M.lic E$|l.rc w@ &i8n d by @npbm or .xp.rimarr.l olFDical 6nift widr
thoe c.ldlrl.d nm itmad n rh.d! rn tt.dM Fl.
Tlr rrPlrH) NMR sFm or 0r @npl.x.! wd. Ecord.d CDCI' rchdE io th.
cxteml €fcrcnce 35% I|JPO.. ''P NMR sr€tsr of aU conpldes shov.d r singL
E5@ ir tlF nng. of 6 - 32.85-26.05 DrD @66in8 rh. ddiEdo of rh.
pnoqniE figind 'ith etd 61d wnich n Mpebtc to liidtub v.,lu6 ntsl
3.3.13 Shgle Cryrtrl X-Riy AnrlFl. of C-8, C-9, C-13 rod C-14P.lladum CoDplr!.i
Th. mmpomds C.& Cr, C-r3 lnd Cla w cry.r.lliz.n by slow diftEi@ ofdi.dtl .i*r inro dE dichlot!ftlte slurio of rh. @rDounds, X-ny '6laconffm.d ! disiortcd lquN planft g.om.ry ol lhce plllrdiun conpl.xe!. T^.
leldtd bond ADd€ ud b6d logtbs rE SiED i! d. T.bl. 3.3.
frbr. 3.2: Cry3r.llosrp[ic .!rrr fd rlE plllrdiuD @plas
CJ ott atl
1., P.,.
^,
A-\ f,r:a
r*lo\f-"d\t'b
"\fisoE !.a: ORTEP dnwing ofdplex C-l with tnemrl .llipdoids .r 50 % pob.bility
FlgrE lJ: P.ctins d.gm ol d€ stJrjtfu of 6mpld c-a
or
,:lto',J4,*
66
Ibc sp.a gbup of C-8 n cnid wi@ th. crysbls BEv 6 mtonorphEnico-iwis ud thc stEiio {npl. us.d fd d. x-ny .xp.nmdi r.s *id.d *il'i0.s I (5)% ofthe molccul.s vilh $e stuotur sh(Nr in Fi8uE 3.4 lDd ih. Est havins lne
inr.d.d stuctor Th. dilin hydbsa Hl in cmpLx C-8 slDvs a hydegd bonding
inr.Bdionbon ofdc chlorir. Iigands .firch.d dnddy ro tlr pall.dim n ld @flcr'Ihc .qu!re pli.li c@dination of th. prllrdiun is rlidrly di$otud by lh. hydFgm
bond (dcDoEd H-bond) b r. sd. ofN-Pd-Cl (H-hond) = 86.80 (T!bl.1.3) wh.6sth€ orha dgl. N-?d-Cl = 89.4' slrcws .lmo* no disionior berw li. iydsgd ltons
ofrhc n.thyl soup !rc 1oo f.r lprn io hydrosm bond b lnis c diD.. I1lc tydbs.n on
th. rrilinc N i. ddition is.lo$l p.rfady in rhc plrft rhough Cll, Cl2, Nl, Pl. This
planc is diddy dilro.ted squE plad, *nh lnc flglcs Cl,Pd,Cl 174 09" dd N-Pd-P:
17s,9q. Th. nerhyl is placed b.Neft o* inlm- aDd tqo inteFnoleulr chtorircs, 6slbM in lhe pa.kine di,gtu Fi8@ 3.tt rtblc 3.2 sho*s thlr tha hydm*a{s) on the
anilin. and 1be cycloh.xyleinc c.!e a siDild N Pd€l (ll-bord) .naDlar dj$onior incodplq c-9 (Figrrc a5) rnd bolh mot.cut.s jn cl:t (Figu,c 1,8). Borcv.r, $edtsbnjd of t.. optcing N-Pd4l dgtc ir iD lh. oppoljr. diEtions mplFn *irhcontLr c-3 b.qu& of m luiribte p.rrn.r rd lryd6!.n bondirs tr vd dd Wmlsmrcmrnons. Inlc{di lhc lolylphosphinc rcl s arts&lor td.h.* cNorin€6. Th, packing
diagnn in figuE 3.7 indicn s oEi qc ot th. tolll4 h.dryI 6tb rlE s{@ b.Mdchlo.ircs siFihr lo thc n€thyl 6 aonplex C{. Il. only nrnsbrioul s}rn ry cl.ffir(c-glid. planc) in comDld C-8 c.ups ihc Eol.cules io point ltnosl in one dnetion.
TrbL 3J: Sel6r.<l bond ldgds (4 lrd bond srl6 (&rr*t oflhc coDpkxd of*llici riDcruEs .c 0ailrbl..
Trbl.3,{: Bord o8l.r (d.sB) of lhr conpl.r.s of}hkb rtuoB,F avarrabr.
ZN.Idal (g.bord) zN-Id{l _ctPd-cl
c-t 86.8(2) 89.4O) r 74.09(9) t7t.9(2)
c-9 36.38{r3) 91.r8(t) r73 6t(J) 114 4?tt0)
35 59(l l) 91 4?(J) 174.90(5) r74 J8(lr)
c-13b 35.33(r2) 92l2ll2) 116.86(5) r78 99(ll)
63
T.bL aJ: Sreifi.d hydDg@ bods (A).
IIII z (Drr|l
c{ 0J(ro) 2.2XtO) t.07E3) B7(8) Nt-Hr.,cll
c-9 0.eo(6) 2.66{0 .).0, (t rr2(5) Nt-HI..'cl2
0J(6) 2io(q J 048(t rm(a) Nl-HtA..C12
0rr(6) 2.7E5) 2.95t(t) 94{O Nl-Hta...cll
0.7(t 2.59{6) l rlt o) r65(6) Nl-HtB...Ct2_lt
c-l.tb 0.3r(5) 2.70(6) lor9(5) r0t(4) N2-ruB..c14
c-lJb 0.3r(6) 2,62\6) r.m2(t) ||(5) N2-H.28.,Ct6
c-llb 0.96(6) 2,41(6) 1.130(t rt8(4) N2.H2A,.,Ct4_$)
llidokcubr sliI]Mid tl - ,s -'aI, -.rt; '2=
-x+ t. -y, -z
r:1"-'i, !:,'
I '.,,')i 3.ao .= \,,,
e fr,ilt 'Y'> i' adr .z..ro tr* 1:3
t"^1Tt"
IkuF 3.6: ORTEP dn*iDS oI mplcx C{ wl|h $md .ttip.oids .r tO % prcblbiliry.
Fturc 3.?: P&king dia8m of ln. stuoE of @nplcx C-r.
*).. "\l-( );;-,r.&t \)-{
'#$';k-a;rixioiire\
)-\ #Ll:'*T
5FtuE 1.8: ORTEP dErinS orcompl.x C-r3 with lh.ml .llip$its 50%
pobobility.
l3
{l)d}'"':i*i
7t)
Dl!.E J,9: P..liq di.g@ of ttE sh.r4 of mpbr CJ3.
a
a"\
..,t lId",4.''5
FAUE 3,r0: ORTEP dFwinS otomptd C-ra wih rh.mt elipei& d 50 %pot bality-
Iti,/(.,
-
;;)i(: l?r- /.;o
-4,'h..r"\:*
rc.\is|
",ub
/.;rot'
rt E3.rl! P-riig dilgM of dE stEnr ofcmpla c-la.
TIE t*o srb4lt iid.pd&d eo&.!l.s of th. 6tfn ri En in C-13 (1i..l3b) show simik [email protected] bodnS chmr.isi6. Th. 2{htN oitine hydosoinr€*r3 widr tlE eilie chldift . @ of d. dldi6 d dF Ftladion innn"
tuL.lLny G *Il c i|.'@kcuLdt *irh .hr.i6 of rightdins rddL. (FigN
T.l|i 3J: Bdd dirht6 to !.lLdim (A).
c{ 2.160(7) 2.25n\23) 2.3r12(22) 2.28$(22)
G9 2.160(4) 22116414) 2292t(t5' 2-2882(r5)
CnJ. 2.r55('r) 2.2J32ttt) 2J123(r2) 2.zm(t2)
c.lth 2.lltl1'l 22247(t4t 2.10r?(r3) 2.290t(t])
f2
TlE squaE pler c@diDad b.ndi of Pd 0I) show v.ry lnd. vanadd hcl*cn
ln. roleules (Tabl€ 3.6), with rhe .xc.Dtior of cl3b which dnibib i tgnili.drshoncr bond of the anilin. niEoscn 10 lh. m.l!l. Ir all doEr cls it is ob*fld lhit th.
hydrs.D bo'dins bdwccD ohlqiDes ind nitogcD (Pd-cll ) .nltBos the 6o.d di.bnc.
mplad wnh 6!t otlha nciDta-ooL.ul&ly hy{,$g!n bondiDs cbrdin4.
A tu,s.d.cr b.tue. rh. tis (oryl) pholph;e lId ln. mjDc ligdd n obso.di.elchoftnccomplqcs, A siDslc bond l.nsrh of206 pr for N-Pd ind 237 pn ior P-Pd
woDld bc cxpelei. How.!d, $. x-6y dllysiB lhowed thal lnc N'Pd bond Lngin of
-216 Dn, s loDger tho .rpeEn, r'd li. !.Pd ho.d ldg0! of-224 pn i3 rhotu $fr.xpeed. TtE phGphi@ ligud is r st nga fald lttnd th.r 0E oirc lis!'n !sddiv.d iior the D..lroscopic sic' Funhcmon, dE phosphine ligdds cln b&k
bond b rh. m.&l whcrc.s tic smire lis$d! urilied do nol. Thus, th. phospnin. ligrnd
cordlMcr noE rb.8ly lo th. ncbl th.n des dE rbin ligrnd dd ihc einc is
'!Gn d lwoy non th. r.nl in lhcp'ts.E ofrh?phosDhin.. Thc Cl-Pd bords *an.llwd b b. -229 pb; rtnl whd i CtPd siDd. bold *ould h. qpete4
Thc lrisG.yl)phoQhine lisand rftngca i! a sbgScrcd oddbtid to nininiz rh.
inEEction b*en ihc chlob ligdds .nd th. ph.nyl noi.ti.r Th. atusd.m of tno
anin. Iisdd 6ies eFc iD@3ting surios of inh,notauLr inhciid. Lit. rl'.plFsphin.ligd4 dD asirc ligbd is |lfuS.d h. ssgad co.f@uti@ wirh BDarto th. chloD lisands (Fi8 3 r). h th. cx.nplc! or c@plac! C-9 ed Cl4, rh. hrye
crloh.xyl doieti€s on ll1. dicycloh.xyl.minc lmAe tb.m3ctv6 in r stlggcEd
conrom.l'm with Gpel to dE chloo li!.ndt ro mininin cowdins (!is. L lo). nrroaion in3lc of $€ Pd-N,H - Cl tsr. for coDplqe C,8, C-9 anq C-r4 is l, 6, ind Id.8Ec csp.cliv.ly (Trblc 3,6) whda for conpld C-13 |n. !m. losio Msl. b $l&r8. as 32 degrees du. b ine &pulsion b.w6 thc cnbro lig ds orld (U) iDd r$c
chlorc 3ubditu6t of llE siti*. If tho lggcEd otomrtion .Iow riic aniEhydbAd ro he ir pl.n. *idr lie chl@ tigrnd .s shom by ih. r6i@ ugl6, wobEfts . Edued disbne b.ero $. mift htdba.. rn<t rhc ch,oD liSr.d nor
wnhbnding a possibl. inr.dclion. Tl. hydroga .t66s on lhc anilinc aE in t3n88.rd confomtion in @npld Cn!, dd witbout llrgc noielies to [email protected] Ih. hyd.og6 rlotu e m ldg.r iD ptanc wid thc chtoo lig&& lrd th.dallJE .E longa (rrbla 3.3).
7l
ln conplexes c{, C-9 ind C-r4 rhc in-plane drgcrar ol the tsinc lieand
with thc cnloo lisard ruis.! tle p.sibility of ilta-noleub nydrqcn bmding
b"Men rh. chldinc md dE rnino trdro8d c tEviously Fcbl drdifltd chlm
lisands hrE b€en d.domhEd r"r Roon.a ct H dishrccs of 952 pn wdconsider.d shod and rhur hyrlrq.n bondin8, and inna molccular hyd68m bonding in
coppd conplcxes was Epon d iD drc nngc of 24G250 pn Lrzr. the disllne b.Nee.
rhc chldo li8'nd dd dc eiE nydrcgm is 268,25q 260 pn for cmplcxg C-3, C-9
a'd C-14 EsDdiiftly dd 2?2-286 Dm lor cmpla C-r3 Glblc l.l). ft$, cmplex.s
C-8, C"9 aDd Cla snow signs of-ak hydrog.n bondina bctw..n rh. chlorc lis.nd and
3,4 Prll.dium (II) Compler€s Contdning Phenrnthrolineend Substituted Phosphine Ligands
CH:
Nrro-P-Rr+ct clN
CH:
Ri4 = rrekiyhidsin4 Etddrrph6D6'8, rie'.brtphcpln, tri'Abyrrhcpr6q
Flgu..3.12: ?.ll.di!n{2J-difr c yl-1,10-pL,ri.thElircXprrosDhin.rclilc-20 to C-251.
ft. mcltinS points ol lh. palladiuD cosplexes C-20 to C-25 conidDjDg 2,9-
diberhyl-I, l0 phaanlhblih. ard dif.rcnr lubstituGd pbosDhire de in E tuge of2r 7 2?l qC. El.ndbl rulyes (yo c. % tt, % N) we dcr.miEd dd tE cul& @ in
clos agemot wirh th. c.lcul.Ed yalu.s.
3.4.1 Speclroscopic Ch.ri.l€riz.tioD3.4.1.1FILR An.tysis
IR rrcqu.nci€s show thc coordinlrid of phm htolin. and diil.Enl $bstitoted
phosphin6 b $c n.l.l c.nEr. 118 det il rluo orlR n.quaci.s aE irclud.d in lnc
3,4.1.2 NMR-Atrrlysis
aH, rC, rrP) NMR sp.clE show lh. coddidtim ol rfi. substirukd phoepninc!
.nd 2,9-.tiruthtl-1, lG tE nihslinc. Th. n thyl g@t next to rh. N-abd ofphcnantholirc which i cddiD.r.d to E p l.dium 6&r slrox a sigDrl d 6 = 3.21
ppD end otncr n thyl gioup! n.xt to dr fi@ N,rbn ofphcn&lhrolinc has c cnnicelshin d 6 - 3.46 ppft. &odric pFrm 6f r,!c phcmrhtolinc lirod ft i! rtE nns. ot6
= 7.71-8.83 ppm, how6, pbb,s of pnos?hirc lisauts rE iD tnc mrs. 6 = 7.21-7.60
rn @ of d. "C-NMR srera ttc 5i!n l of bcrhyl gtluFs of th? phGphitu n.r 6 = 2r.6 ppo,.nd Mo n.rhyl g6uF of ph.mtnFlim lis.nd.ft.t o -21.4 a23.4 rpn. Thc lowd ch.ni..l shin vdue ofdE ncthyl gup dr ro O. [email protected] N-.tom of pheunrhbline as conpdcd lo oth.r n.thyt goups (next 1o fi.. N-abD ofphcmn$rclin. li8!nd) clady 3ho*5 thc c@'dinrti6n of l|l. ph.turbFlim lilod b lll.prll.diun c6r?r. nc roDlic cdbon m !E ir llE 8 8. of6 = tu.7l4l.7 ppm.
Tne coodinlrion ol a phosphinc lised is indicrGd iD rh. I p-NM* spahn widl s
sigBl 6 = 26.? ppD. sinitdy, cb.ni6l lhjtu of r'! in lll mririn8 plltadiuFcoDplq6 @ld bc Erdcd. orb.. r.trrdiun [email protected] m.r.inin8 $b€tituEdphos?hincs ud 2,9 dinethyl l,l0-phd.mhblin. show . sinil& behlvid in r,\. LH rnd
3.4.t3 Silgllcryst l X-Riy Ardysitfi. crysbls of Pd i2, 9.dim€thyl-I, t0-!nd! h$li*Xtri*n-
ldylphd+hi!.)C1,, IC-221 *d. eDM hy slow diffrljon ot ed.nol inio ihc
dicnhorcthrn. elutim of ri. pil.di@ cohptd. Du* r.d crysl! *.d obt i*d.Th. ORTEP di.grlm of th. cryrut i! shoM b.tow:
1.. e./ -i:.,\-rts /_ -i )'{r
..1-1. "il,iv-r""\T, i I ttl ,/ct
")":f-{i .Ti-tp"t
"!-,ii.ft--r.""..2.-.,i.-ri --4.t"r''"-;FLUE 3.8: ORTEP dnsirg ofampld C-!2 witn rhcnMl .lliFoi{Ls !r J0 %
Pob.bilitY-
IIA.E l.rat Pacting di.gtu ofrh. su.tuE ofomtld C-t2.
n mlkx crhabic dirotu<t ,4@ pbru smFy du. io rh. b!!(t tiguds$Ltnitur.d pr'.fulhblinc od subnitu&d dftlhin s. TL bood Mgts N (tlPd-P (l)odc(2]Fkr4(l)e 172-20 (t8)&! t7.28 (8). KlfPd{(2I N(t}pd-c(D. p(ltRrc(l)!!d C(2!Fda(l) c n|mrt*.1dstft.nsL io andtlrs i.<r@Ld by
9l.42 (|6),92,76 (8),35.t|! (4) od 39.83 (r, Thc boR lostn ofpd{t(t) is lons.r rhePd-N(r) ed Pd-P(t) by 0.t74 A o.o?74 simitstr, bond tcngrh of pd-cl(2) is loglrlh4 Pd-No) , Pd-ptD by 0. | 70 A ldt 0.073 A.
T.bl. l.7r C4/tblloSnDhic ||l0 fd mDI4 Gt.
Cryc.l StsE r, spg 8roq
F, &g
RcnFdNColLcr.d/U qs
Fi'.I R iidi6 [F2o(I)]
RI
llwR2
c$HroNfPd
689-90
r30(2)
0.710?t
9.6sr0(5)
r l.05rt(or5.9855{r D
tsr.515l2)
,1.529C)
r08.@!o)
r568,6qtO
2r.461
991615621
0.0650
0.!r6!
0.1652
0ta3l
n
B.d l.ngih(A).d Bold A!sl$ O
?d0) N(r) 2140(6)
2.237(2)
2.r0(2)
Pd(r).c(2) 2.I4(2)
N(r)-Pdo)-P(l) l7].r0(r3l
N(r)?d(r)-cl(2) 91.4206)
P(rlPd(i)<(2) 92 76(8)
P(l)-Pd0)-cr(r) 8t44(l6l
N(r) Pd(r)ckr) 39.31(7)
c(rl-ld(r)<(1) r74 23(3)
T$1. 3,3: Bond lda$s lnd bond angl.s in t c.ysLl of comll.x C-22
3.5 PyrimidineBenzamideLigrnds
.rL s 9 7:r( )LN-c1 /-RtsR
R = Cl, OM., R/- Cl, Br, Mc
Flgrre 3,15: Ptdnidin -B.tuid. [L.l ro L-5]
Differcnl $6s1itutcd N-prrinidinc-bmzanid. cmpoundE weft syni\cliad wir\good yiclds of 72-34 o/0. Elcmcnlal anlltss (C, H, N) wcE dcbmined and ir was
ob*d.d $tt fon d lrd clldl.r.d klu6 .E i, cle aeE.mnl Ih? trlrir8 poirr ofill synlh.siz.d compounds !E in th. mg. ol 154-18? t.NMRAulysis
Ilc fom.rior or @npouds w.s lssed by |H-\',MR and LrC-NMR drE. H-
NMR sp.ch show rhit dE pbro of N,H Esur.s !r 6 - 8.05 ppm. nE roirticpotons of fi. b.tui<L ring @ in th€ tugc of 8.96,8.94 ppo md dr. th.r'yt n g
rcsoninccs re obswed in th. rdge of6 - ?.79-3.6t pptn Orhci conpouds foltoq iE
73
en. bd. L c6e of hdnYl subsritulod conpounds, ndlryl ptoions show al6 = 4.ll
pDb cheEicrl shii ud for n.lboxy subditukd coDpound, Fclnoxt pbhs apFat tt 6
= 1.32 ppn. rrC'NMR s?ccts! l|e Eql 0E fomlriot of t ffii& c@Doulds Th.
$.bonyl €$n.n.. was .$ign.d at 6 - I67.2 Fpn .nd the ca'lon liom of thc t€rnid.nns dircctly atllchcd lo N-H gbup was obi.fl.d d 157.? ppm. Olhcr conpolnds follow
$c se pan€n of rrc-Nli{R values. In c.* of.hlorc, brono lhd m.dvl substituGd
cornpoundE .hc elon.nes ofeftonyl gouPi rp!.!s 'r
6 = I67 20. 16?.86 dd I63 21
pps. Ito*eva, in cls of4.Nore tnd 4.d..hoxy suhsrituicd 6nP.unds lhe @rn nvl
gt@06 sho* sigels { 6 = 171.6! and 167.49 pDD. Th. cbdical 5hin5 of the minihgc.rboD atoc d. in rhc nns. of 6 = L 10.3.1 t8.8 p!n.
3.6 Pd(PO-OMe)Me(Py) ard Bsse-free Pd(PO-OMe)MeCat{lystJ
odo'-evoFi8I . 3.16: Pd(PO-M.OXMr)ry
Palhdium (P-O) d<t base fi@ pallrdiuh (P-O) seE synth.siad accodi.s to th.
liEEtlE nclhod lrr ra ''. Firsr the lisand (ehe$oxy?hosphino) b.Mne $lronic rcid
wlr syndcaiz.n sd ch.dclerized by rl-NMR Tne 'H-NMR Esuln of litdd, !d-codpld rnd .le b& &e Pd.cmdcr s osisrai vith pEvio3ly Epon€d lulG.Pd-M€ Ep+ !!5@l. !t 6 = 021 .nd tk OM. gbup atD.r. !t 6 - 1.67 ppn. 118
rclont*e sigtul of Pd.M. in ce ol tn. b.* n* ?d{onpl.x is ii 6 - 0.4,4 ppo. ntchcmical shins of lh. m.inins DbioG a6 conplbblc to lit€mtor. vrh.s F{ rrl.
REFERENCES
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whic. A. t. P.; willihs, D. t. L4 n. Cten. Soc. t999, | 2I , ana.
5 BliiovieL C. J PiGibso!,V CrKmb.ncy,B S.tMadox, P. J.tMcTrlish. s.
.r.r Soh'L C. A.; WuL, A. I P.; Willids, D. J. CTren Conu u. 1998, 849
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3 Sun,W lr; arin& S,i Zuo,w. C, k C^in.zc{d,l1,301,
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10. ljinc, T. v.i !inor6, U.; bppallircn, K tKling!, Ml Ailoh, E.rtakch,M,J. Oryonoha. Ch.n. ).000,606, I l2 .nd d)ftin rfceno.s.
ll. Ji., S.; ZE& D.: an& T.: S!n, W tl.; Cba, t.: R.n, Q.; Liu, D.; Zlcng,6.jChd,w. J. A4o,on.t. Cten. 2@5, 690,1739.
12. Sun. W. H.j Th& X.; Gro, T.; Wu, Bt Zhina, W.l Ma, H. Otearcneblti5,
13. T!nl, X.; Sun, W. H.j cao, T.; Hou, J. Ch. L; Cha, W, O's@oMt. Chen.
14 Sn, A.l Zhlo, J ; Cui, Y.; Lian& Y iSun,w.fl.SrEr, Canrtu. z00s, J5,23l7.
15 Su. w H. ; Hb,?. ; Li, G ; Au& Sj wd& \v.; Yi, r: A@, M. ; Tt4, N.
J. OrAarohet. Chen.2001, 692,4506
l6 Adcuy| S.; Li, G.t Zhrn& S; Wft& W.; Itao, P.i Sur, W. !t.i Tte, N : Yi, J. J.
O.gotuaa. Cha. 2001, 692,1512.
17. Chcn, Y.r Zro, w'; Hao, P.i Zhang, S i C,o, K.i SDn, w' H.I Oryatuhd. Ch.rl
l8 Sil]3cr, A W.McElviin,S.M.t.J 1n Chen. Sac.1935,57,1135
19 Bd.s, R. A.j Falcs, H. M. J. Ai. ChcD S@ 1953,?5,3830
20. Bncb, W; Mich&rb, R. ,ern ,t Hdndboot of Ctganic ch.nittt , 5n
supptenenta/, wi.t, Spn^$-V cn!s, Bdlin, 1990, 2r, Pld 4, 128.
21. Giln.nn, B,j Blar! A. H. Ofa. Sr?r/,. .Zr. Johr Wil.y .Dd S@, trc., Nry yo*,1943, P6t,
22. Dc I(inD., N.; Dc Cet \v.; Sch,hA N. t^da,r, r 937, t 33.
23. Asm!, M iAdeuyj, S.; Ktu€, X.; Bodshah, A.i Su, W.-H.l€,. OrA Cld.
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28 K.linowski, B. O.; B.rger, S.j BbM, S. .BC-NMR SpeLro$opic, Tti.ncVenag, Stung.4 ctuiny, 198a.
29. tubnd, A.i Nesri,S.; lrinripznd, A. Eur J. rnoe Chen 204s,63r.
3l
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Koid., Y: Bd! S, Gj B,rrqr A. * [email protected] ,1t,22rt.
(i) Rsho, F. D.; M.L@& R.,r.ra Ct .r r99t), C46, 5E4, O) Bjur, J. C. M.;
Hirchl.y, S, !.r M.tcau, L ; P.dor!, S, Datro, tr,ro. 1006. 2316, (c) 6itton, A,
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Rodriala-Mrnin, Yj RuizP@z, C, Drl@ laB 2oitil, 2?, 189?. (O Fjv.x ,.C. M.; Bt!ll|@, L tDts. Cra. !9t, JZ 4756. (.) Autlo., c.; BetL,v, D.:
B@, L; BNioA E, A,; ODa! A, A,Cn^ CMm. r9'E,6 6$.
Kfthi. T : Y@hinur!. K.: Noaki.k Dokoh ftad.2006, 1,25.
vcra J.; Lica, c, L; Sb.4 Zj .to.&r,R- F, OtsawkAht.2OOT, 26,f624.
bD, s; v.L, ,,i Li.f, c. R: tont 4 E-F.J. Am CtEn. Sa.NL r 2s, gq{n.
t.,
82
OLrcT)IE|EATP'1,FOw',A.ElTpn
NIT'
crF ntmtrnc
Chaptet - 4
ETH}'I-ENE OLIGOMERIZATION, POLYI\{ERIZATIONAND COPOLYMERJZATION
4.1 Oligomerization ,nd Polymenzation of Ethylene UsingCr-Quinoxalinyl Catalysts
4.1.1 OligoneriatioD &d Polyn .lt tio. .t lrtm Prsure ofE.hvl€o€
Castn IC-21 (5 !ml: O OO25 s) wrs dGslvcd in rolD* 110 nL) in a pF d.icd
S.hlen} Nbc along wirL 6Bdt 3titrirg uDd.r d ahyl@ pBsW ot I rh Th.
E.cnd hpcmtuE 's s.ifiimn .t 20 "C rith . wal6 btih lhe E.cnon wr!
iniriri.d by rddirs lne desiEd mou.l (2.63 mL, or rs indimtcd) ofco{5Llvsl Atut l0
min, i smoll mou.t ol dE lglioD mixtut w.! coll.c&d wilh . slringc Th. rclctioD
w$ qu.nohed by the addi.ion oi 5 % aqu.ous Hcl. nc olig@d dislribulF! w3s
md rcd by ss{nrcnalogrlphy (Gq, m. rmci rg olltion vs qlenchcd wilh
acidificd eda'ol (s 7t. Polrtdryld. fom.d q.s tltu4 w.sned *ilb .0Enol, d.'.d
undcr vacuur ar 60 "C, wcigb.d d ch!6cl.n4d.
{.1.2 Oligoheriz.Coo dd Poly|'tcrl4iioD .t l0 rtu Plsutc ofEthyl.r€Hign plts@ otison riztid lrd FlrDaiarid E.dios w csi.d oul in !
250 DL sEinl6s stel ariocl.rc s.1or cqlipt d with ! nshdic.l $iM a .rh.moslrr The scto. v.*.1wrs dncd in rt ovm prid to.ach tu and p4!d wirh
vrculn N, ihE.limes. lt $lulion ofd. otllylt lc-21 in lohde (r0 'nr),
th. co-
@nlyn MMAO (2.63 nL) md lolu.nc (70 n!) wcE rdded b $e Bclo! v.$cl undcr
ctylcnc atnosphd. wl'm $c ftguirld t mp.dtuE Nrs obtrire4 etbylene (10 atn)
wa. inrrodlc.d ro start the '@lion.
Tho dction wd slopped aner 30 sit. A srull
,nonnt of th. €aclion solulioD wls 6lLoLd vidi a 5)dng. lo @lyz rhc oliad.rdisEibutio srd [email protected] by adding 5 % rquols HCI $lution. Th. €m.inins solutjon
wr, i.mieEd rddins d !cidi6.d HCI ..hml (5 %) elltid. Thc polrla [email protected] *.6
filr.Ed. wlshcd vilt €rhel. dicd umld leum .t 60 'C to c@sn w.i3[ w.'8t'cd
83
4.1.3 Ethylrlt.OligoD€riz.llon .nd PolymerlatioD witt MMAO at I
lisand architecture bd raclion oondilioG havo s grit innum* on $e clolltio
rctirit or all conplexes In cle of dkyl'substnur.d li8.nds, tlE e.ndal Eend of
incusing Erivig ir atal'€E is C-l < C-2 < C_l < c4. TlF oligoner ditribunon
ranScs fron C4{2& In ce of h.logcn subsris(d ligo& ln. }E Foductiriti's
dccre b trle l*ls In ou.e 2, 6 dinllMjue substhi€d ltSod @nhining
compldg prodc.d only digond td no polF6 Thc compls ch€ltLd with !uin.tlyldilin. slbglltubd liB.td diglly.d th. hirlen lcnviv Mosr pob.blv rh'
m.thyl gtow i. th. p@ positi@ ir plryin8 I !igDi6m( rol. vhich is cod'p|Eblt !o thc
E.ulrs EDon d by Esh.ls l'r,
4.1.4 Innuenc. of Temper.lure .Dd P.63ur.Cadvric 4tiyitv s srldi.d !t did.dnt AI/C! Btios. Il was ob@cd tnll dn
incrclsins fie Al/Cr 6do imprcves oligomq fomddon lhe higb.s 4livilv wis
!chi.v.d ot AVC. nolar 6rios of I OOO. ll ws lko obswed &al tne PE pbductivitv was
.nnift.d lircely virh rh. AVCi nrio All lditing o@Pl€x.s wft studi.n usi4 tr
Th. €clion resFEtln hrs ! t n.nno6.Ift.t @ thc lclivirv Bv iM'nsrh. r.mFtuE, fr@ 0'c io 6dq lh. rctiri9 i*qs.d liMrt. 11l? rdshd &t'virv
*as ohbircd al60'C. How€wr, 130 oC thd is r ddic d@ oflcrivilv which ir
D.rhaF du. lo thc &di$iion of atir. siL. by d4onpGilioD @tion oI dE cabrvsc
Thc ftnd E r.pon€d pFviosly by our !rcup cl.
4.1.5 Ethyl.ne Oligomed23do! rnd PolyEerlz.fotr with MMAO ttHlgh PmsureAII cdhpLx.s tc-ll lo IC-71 *.E stodi.d ror olison.i-rid and
povr.nadon of.thyl€rc !t hidr pE$urc. Th. r.sulrs aE sunDdiz.d in bbl. 4.2
which Evals ihri bisl pEssw hc . dsnilic.tr .ffd q rhe ci6\tic lctiYilid of .ll
conDld.!. To *l€t lbc b6t r.spd.of r ! nigh pElsE, alalF [c-4] vamplor.d. I1l. E$lG d@Gdrc tur (C4l folt@d rh. s.e tud .s obwad .llrh Th. hisncsl eiiyiry wB rchi*cd I 60 !C *hich i l0 nDd hi3rld du. rirobriid .r I !b. A[ remlinirg conDldct w.E 3todicd rr 60 'c vidr d avcr nolrr
ntio of 1000. Tn Eacdon dn vs t.pl c@uDl durin! lll cipsiD66
34
At I0 atn @npl.x, IC-31 cLl.tod by m i$prlpyl @Einin3 listld L8low!c1ivit. wlich 3.@ to b. duc to tn bultinc$ of dE nopopyl hoi.tv. Morovd.
Mdd C-5 wilh 2,6ni0uoMiline ftuiB its s?enliv bv siviDg jrn oligomds'
Nhich is ooFptabL to lhc lHls oltlin d At I .b rthlc oth.t con:plexes' .xhibil
diviri6 Iotimeshisb.rrn.dd.rI.h-AtBEhhtldPEsuE(20lnd30tuD)thccihlni. bcnayio. of C-a *$ stodi.d. Hig) prcls ddstiglly il)@sd thc PE
prodlcnut Indeed, lOrtn$e.abl'3lfsvfyras27.2. loiS{Pt mol Cr) hi
4.1.6 Ch.racteriador of Poly€thyl.ne
[email protected]!i6c! quttaaofpolysd.Th. D.lrins Doi vllua ol ln e Fryffi derdin.d It ditrmti.l singcrbnm.B aE coBirr..t wi$ rhc hhcs obnin.d ior EDPE lrr
T.ble 4,r: OIsom.ri-iid dd PolttunaiioD ct I oiD of Ethtltu *iih C-l loc-?/MMAO.
cffil cdddm: trnol {ri dhyrm gE!€ , 6t Tift 0.5 h: Tduft 30 nL. li ui! or rd!(ior .f crtih i ' D.'mii.d by c,c ud cf-Ms.
r(|c)
35
T.ble r.2. Oligoddiation qDd polyn.riaiion ofclhyltr at hilh pc$ur *ilh C- 1 loc-7/MMAO.
G.@l Co tirio6: ClLlyd 5 ,6ot e$yra. pt!3s to .d; Tihc 0.5 b Tolu.m tOO
mL.'lnunit!of lO'8(ool of Cr)rh-r tD.amir.dbyCCddCC-MS. (In udtsottOJ
4.2 Oligomerizrtion of Ethyl€d€ Using Paltrdium(Il)C.talysts Containlng Mixed DoDor Ligrnds
DiftHt prlldiuD cordpl* coni.inins ob$jtur! phtunrtrolirc rdphGlhinhxazolim lisinds have b€.. r.poicd lo prcluoe edyl.n. olisond l4rl. Thc
doliil.d nebanism of cthylqe oligoicnaion by Btiodo p. .diun @nplox.scoDEiniDg 3,5'Mcr{lynalyDcEsi(plolyDt w6 iftstis{.n by Jordo,s srcuD Fl.
To thc b61of or Lwl.dg. dt is rhc tulr dm w brE usd p.lidiun cdpldevtlh nt\ed doM lig.lrL fd rn. oliS@dialin of.dlyl6..
rcc)PE
%)
5.19
2 l0 21.5
J c-4 30 0_45 063 58.1
c.l 60 IO 0. tl 39.6 015 l0.l
t c-2 l0 0.16 39.9 l0
6 c-3 l0 0.019 18.2 0.19 2t.7
0.62
8 c{ 67.8 0l? 32.1
60 0.10 78.9 2l
t0 20
II 20 2t_2
36
4.2.1 G.!.r.| Procedure for Ethyl.n. OligomenatiorA fully dricd Schlcnt luh. coilining rhc Equirod aDourl ol coblyn was
.ltcuarcd and pure.d with nitugcn dwo lincs Thcn .dryl.n. ws ch.'g.d rwioe.
FEslly dnnlled lohac was .ddcd and srircd for 5 hin, b dissotv€ the cal.tlst. A
calculated inount of ooo.blFt MAO w!! .ddd via a pr.-h.ard ftd prdried glass}'inee. lh. Mclion hixlur. wls lriRd lor 30 min und.! I rh cthyl.nc pEssre. Aiicr30 m'ruEs, rhe uction wa tcmitul.d by addine &jdificd wlrer (5% aq!ea!! HCt
solutim), IE @clion limplc vr5 an.lt&d by cC, fte yietds of otisonm w@calculalcd wirh r€ferenc. lo th. tu$ of rolv.nt prcrcqujsic $!r thc Da$ oi each
tuctio i apprcxim.t ly proponio to n! iricgnrcd ac. iD dc CC naE. rn ord.r ro
.liniBte tE chdc. of f.l* rctivir, d.Lminarioff du. b dhpotonion,lion ol $e bis-
Iisabd conpl.x.s (silin. .nd pho$hirc), b.ih [pd(phjp)r]Cl, a'd lpd(silinollcb*cre qaBrncd scpMi.ly b.hck oli3omniurion of.dytce dd w.E found ro b€
nuch l€$ actiw rhan rhc nn.d li8&d coDpl.x.s.
'.j-cr. vro1lE
S.L.E. a.1: Mod. of &rion of dE @rolysr MAO
Thc prclE n nod. of &dd ol dr. MAO coqr.lyd ii lhos in Schne 4.t.Ir. cdtalyr MAO 6Rt poduc!! an ioDic p.n vnn lh. eulyll. This i! @rsidcEd sadivc sp*i6 in lh. oliSohcriadon ofdhyl.rc.
4.2.2 Di.cusslorTables 4.r &d 4.4 smnlriz vfious conditios ued io {tct mi.. opriDal
cablyd @nbiMlids, caulyst o'qtdrions, !ftt E.ctid tdlP.nlur.s io oligonqj4.$ylene wlrh palla<lium (II) onplcxcs. Tn. rcaction condirion! w.E el by sel@rina
suihbl. lcrpeEtuEs, co{autysrs .nd tinc. DffcEnr co<lratysE (MAO, MMAO,
EnAlCl and El,{lcl,) w@ slbj@cd lo deEnin. th. co-clrrysr ofchoic€, MAO w$sereclod duc to tu hth rctivit, with C-8. I'!. b..t Arlpd conccntslrion *rcct.d Ms500. wlo tb. AVPd Etio Ms iDcasod rborc 5oo or daq&d h.low 5OO, thc aclivigdrop'p.d. Sinildly, c-3 w6 sbj.ot d ro cvaludc rhc bc.r Fo$jbL tdpsarD!..
37
Ar 25 'C rdFE@, C-8 show.d th. tigher &dviq vhich was dd@s'd
$heD ttF hFle irca*d. tik.h.ng. nish b. du. ro th. ddonpositid ofthe
.cdvc A..i.s !t nisn r tdFnoB. A! shoh in Trbl. 4 3, l@ii@ pamcl€F lik.
tine, hpeBtuE, pr$uE .nd con@nhtio of rcebDts *cE k pr co$lai ro allow
compa.i$ns. I. order lo.linidc tlc ch!n.. of .mt in dallmioing $c acnttv dl. to
$e dis?bponiomnon of bis-lilatd conplox (r.ilin. and photphine), blth
I?d€hrP):lcl: ad tPd(anilinc)?lcl w.e cxrnin.d stdt lv to ch€ck lhc
oligohdiztion of elhyldc. nEy wcrc foud to b.lc$ ccdve than tie nix€d ligrnd
conplex lrdPhrP)(anilinc)Cll. Funhd rcsultE rcv.il.d ihllb, kc.pins lh€ proM
phos?hine ligrnd conslant lnd chsnsing lhc substiluLd anilin. c,auses a li3/lificant
cblnse in cabMc aclility. Aclivig incEr$ in dE ordd oi Cl4 : C-9 < C{ < cll
Trbl. 43: c@t0lyn Scldtion fo! oli8om.rialio, ofElhvlcto bv et.lvBl c_3
CeneEl CdrdiiioB: 'lo' gmlr.tnihnr.np. 25t, Tolla {lOnL), Ilhyla.
Drswc = I ah, Tidc = 30bin., C.r.ly$ lPd(PhrPltnilin.rclrl, = 5lmol C@dFtMAo = Me$yldubircxdc; MMAO - Modifi.d M.thyldudimhq DMAC =
Dim.thyl.lMiniumhloli&; MADC = M.lllyl.lbiniMdicnlqid.
The abMc lcriviry follow! .aording to rh. *rucruE of the ffipL*Spccficrlly tb. cmpl.x.c mry b. SrdFd ..cording b ln. smngeoeni of rh. .niftlisand. Th6 e a& abl. to sumkc lhlr th. n!tuE of dc miE liSend pkys . d€6,itiw
ole in lrow acrivc rhe 6t6ly5l colld b. bsards ol.iin oligm.ri4tion Cabllt$ c-3,
C-9, Cl1, lnd Cl,r have an aninc sisctuF wnh brg., hindenog mojcli.s that enhand
hyd&gd bonding b.twean thc.nirc hydrcloD tnd thc cnbb lil.td t6 6bom in ltE
N.m pbjecion ol lhc miDc lis.nd rclidle to th. chlorc lieFd! in cahlysts c_3,
C-9 dd C-14. th.e lolr comDld.6 cxnibn b*d clt lltic aotivin6 (Tablc 44)
Compld€s C-10, Cl2, C-t3 hd a cblob- .minc liSrnd without legc ii.dding
noieties. Tlc aDire hydrcscD- 6d chbndc !loh! w.rc rdanscd shggcr.d !o th. chloE
500
500 0.24
MADC 500 0.t2
33
li$nd! ol $. ?d 0I) and stos.d tu in6lmleula b'dFser bondinS Tha*
cmprax.s.\nib lrb ciblFc .q'vrB (tibl. 4 /t)
Wnil. lh. sdcM of rhc @dPI.x cofrh@ wtrh casllric ctivitv' wc
inv.stigd.d oihd €lcctonic contriburioc tn.t ln. lilandr h.ve in deMinits l.tivili.s.
Thc citlltti. activity incr.6es i, $e cds. of chlob sulslitntd iniline irdiclting rhar !chrrsod ligdd eDvenb.nl abmd rh. n.l!l is affciits lhe &tivig of dE omplcxc6
Ih. pbduc?d olispnm @inry c@iscd of buLn.. Th. elivity of C_12' whicn
consisE of l.5dichlo'!)mline is L6 ' I or *nich i! sr!.ia $,. ib.l oI @hpllc cno
Md Cl3, {nich hld c @ $bsritutio o dE Dch ud onho posilio4 a tl.!.ibl..xDLrdon G lh{ u clccrls vil[&.viDg Gftcr of dE chloriE ndF o eiliE niSl't
cFr. .n .L.86 &6ciency on lb. bcd cd6 ehirg in ! DoE.laroptllic ndlcdtd lht mish dnftn highd slivity. Md@ftr, r cdrplq shctuE f.vs chlin
transf.s Gsulti.g in oligod.r production,
Trbl. t.tr Reicti@ prtrcL6 for oligmonznm of ethylac by Pd o.blylls.
0r^ol/Pdl500 1.00
, c-9 500 0.70
I 500 1.50
c-l I 5oo 25 t.l0c-12 500 25 1.60
c-$ J00 1.40
7 c-14 500 25 068
500 035
500 30 0sJ
l0 500
lr c,3 100 25 0.20
3(x) 25 0.25
25 0.?5
500 25 r.3
t5 500 25 052
ccid.l condnioilr 'l0' crtrol'rabn-rhir; tihc = l0 ni4pcs!rc I arni Tollde 30 hL, . - [Pd(o-iolyl),]Clr, b =
9' .l lo.tn.$yl* F.suc.
Catdysl 5 lnol Pdi Erhylcrc
frd(eiliDe)tcl2, c.8' & c"
89
Thus, w. r. rbL b pGtolic rhrtl
vinyl ir insn d into tI€ conpl.x by w.y rhar involves ihc min. lig.td.
$e mlulc ofbond ud stuctue offic lDinc lisrnd dettuinc6 th. activig oflhe
comDlex lor ol.nn olisosenation
hydogd bondiDs b.t**' dE !nin. dd chlm li8Ads
hindr.rc. sovms rh. stucr\lE ofdp Pd ([) conpla.s.
a s33.€d mnA.ndr of th. anili* lydhgd and the chlNelectlor wilhddwal iim tne Pd (II) pEDolins ov@I crid\aic
o c cl c
b c
Ficure 4,1: N.wmrn pojectior ollhc asin. lisand Elative lo lhe ohloD lisMds (a)
conpl* IC 8l Cl-H distlncc 262 pn, (b) omplrxcs [C-9] ed [Ct4] Cl-H d lne 268
pD (2), 252 pF (7), (c) onplel 6 Ct,H didrc 2?r,286 pn.
4.3 Ethyletre Homopolymerization and Copolym€rization(PO-OMe)PdMe(Py).nd (PGOMe)Pd-M€ Catalysts
4.3.1 HomoPolyne.iz.tioD of Etlyl€ne al low EthyleD. prsslr. Ning(Po-OMe)PdM€(Py) aDd (PO-OMe)PdMe CatdystiIXe (PO-OM4PdM.{Py) citlly$ hls ben uFd fo! lnc polymqiation of
eihylft dd copoltfr.riatio of vinyl chlodd., lintl fludid.,.lkyl.thyl ..hd. vinyl
bmidc vili ctiylcD. E tr. Po\r6 Drduc.d with rhjs canrysi e lin@ oomped to
brntcbcd polyn.6 obrrin d by diinin. Pd c!!lrsr5 trq. In cis. of lEvioldy stodicd
copolynes, $er. i5 m inrhrh iMrDonrion oi 6-m6omq units. llos.v*, diinine
Pd catalysts prcducc bra.ched coFolyn.n rirh cenonon€r unns ploc.d ar rhe branch
ads. Olr mlin obj@liv. *6 to dplo& ,.w dd inhsring prop.nica of c.polynmlsing difr.mt dlyl cehmmm hrvirg lddjrioml Cn! ui6 vio! 6lmiionrr golps
A pEn ic.l Fi*lEr-Potu b.il..quipp.d with ! $inDs bd w.r cnns.d widr
the eralysr (20 !nol,0.012 si.nd d.i6d toludc (50 rL) in r elov. box. Th. bodle was
rsmbled dd codct d *ith oE.rhvlm lirc. Thr raction Di:tuE *B hoted at 80
"C for l5 20 min lo dissolrc the catilyd cmpl.t.ly. Thc Fi$hd-Pdd bonl. 4 .h (50
psi) was Diasuri-d wiln crhyl.n. and laror on dcnand to nainlain . pP$ur. of 4 ah(50 pi), helted ar 30oC ror 2 h ,long with oonstrnt sridina. Aner tho rcqln.d reaction
time, dE edylorc spply w6l€minrcd .rd lne boldc re lllo*cd to cel dom ro
dm lcnp@iur. Th. $lvd wa mDontcd rdd v.cuM- M.OH (20 6L) waadd.d b Pleipi!'. th. F ner. TlE pol,ffi obiincd *a *.*.n with CH:CL (20 r3nL), &.ronc (20 t 3m!) .nd M.oH (20 r rmr).
Finl of ill, conEoll€d hmopobm.liarion @clids of.rhyldc Nlg discrlc
Co'MeO)rdM.(Py) lnd be-aa OGOMc)PdMc olllysls wcrc iDvctilatld. ]tuEul6 sho* thd .t 4 a[n (50 psi) .rbylda pE$@ iD toluo. {50 6L) !t 80 'Cr.nFrrtoE, rh. polycdryl* produ..d ,r! Iir.s yirh low n ttryl bmchd. Ar 50 psi
elhyloe pE$urc iD lolla. it 80 'C, low hol.culd veiel poltcthtdc wa, oblaincd
(.ntry I, t!bl.4.s) V.la, Uel Shd and Jord!, irv6bg.r.d d. homoporyD.nation or
ethylere ir detail and Epon€d a tuchmisn ior pollmenadon ot elhyloro which is dle
ro €periiilc inenion of .thylm oi Tnc Ectior lin€ *s fixed al 2 h Snltl .Dourof ! 6lock FeilihE Ms ob*ded du. !o Pd! fmrtior TIE polycthyl@ podued by
dircF (POOM.)PdM{P') dialysl is du. b Epctiriv? irstid of CH?=CH1 dir inlo
(PO-OM.)PdCHr{IIP spei6. Thc TH.NMR Ac.ta cldly fio* rh. sisMls ofr.min.l (PcH:cItr i,0., vinyl sbups) aDd inidd (PcH4lP) grcup! wh@ P =
D.\m.r ch.in. Thc$ E$lE e cmpambl. io pEviously publishcd &sulrs by our EbDprrr. Ille po\alhylcE w!5 p'ldeed in L22 g yi?ld ind nunbd lvc6sa nol4ulft s.ight(r1'./ ws €lcul.Ed &cordiry ro 's-N\rR ehich it 5.6 r rcP. Poly.dtyl4 obbincd by
br*-fie dl,lysrs hc rn ,Yn yrluc of 7.8x l0'.
4.3.2 CopolymcrtzstioD of Ethylele *itt No!-Poler Co-tnoroD€n (AtLow Ethylcb. Presure)
A plcdricd Fi6chcFtorter botrlc wa charS.d wib er.lysi5 (20 !nol; 0.012 g)
m.sndic sti ftd tolu* (50 nr) in slow box. 11 w6 Mblc4 ula our ol rhc slowbor Md cmcd ro e .thyL* $pply liR. Thc *hol. .lhyLe pply Ls *.s.scDabd r'd th.. niEoga pls Fled thbud n tbe tin6. ft. Hciio nirn@ vdh.aLd 51 30'C foi 15-20 nin ro rErc 6uE rll|r d'c @ralysr w* dislv.d cmpl.@ly
Thc co-noiotocr (15 nn.l; 1.8 g) ras.dd.d by s sliins. llon,i wirh a conlinuous
supply of .ihyld.. Lter oD rn .tlyleDe prc$ue was maiDllir.d al a aln (50 Fi) ficddioD nntur. wG hat.d.t 80oC dd8 witb .l)Mrt $irin8 tu 2 n. ARcr rhe
€qdEd titc p.rio4 n w.s .llow€n to cool dos. Thc slv6l *as *rponl.d and
MeOH (20 DL) was addcd to FEciplbr. rh. copoty6.r. nD obr.in d polynd *as
*ashed wir[ CH]ch (20r 3), i€rone (20 x 3) and M.OH (20 r 3) and dn.d undd
4.3J Copolymerizrdon of Ethyl.rc with Non-Polrr Cemoron*! (AtHlgh f,ihyle& P!.sur.)
At vrrious FsuE 4-20 fn (50.nd l0O psi), clhyl@ polyncriarion ws
Derfm.d in ! 100 nL sriinlc$ sLel P.tr tublavc cq$ipp.d wnn . var.r cooling lmp,
lhmooouplo,.rd mgD.tic ly colpled sliftr and t€np€dturc atrd otltion controlled
by a P,F 4842 .orlrolla. Ar rulocLv. gh$ lind ffi chfu8.d wilh 6. c!6ly!r xrd
d.red rolu.n. (50 mL)- It wa plrccd iNi.L tb. sclo. tud va @bled TIE .urocl.Ererlor wls bDushl olt of $c slove bor.rd wls attloh€d wilh tlE controlld ind lhe
ethylcne iupply lin.. The rcnpqrtlE ws nlini.incd .! 30 oC and th. bLrion wr! 200
am. n. Eetion bnne w.s h@&d rd 15.20 mir to mat suE coDDlet. disluliotof dE c,Llt l. IlE cenonmd w.s add.d vir . !Fn'8c llon8 *idi mdtud! supply
of elhyl.o.. Tic Esotor qli pEssui-d vith cthyl.n. till rh. {icsiEd pEsor.20 !h(300 psi) wrr !cach.d. Anlr 2 h dc etbyl.n. supply was temitulcd ed de pr6sE was
*ld*d, Th. r&tor v6 rllMd ro c@l dowr ro im (dp.EtuE. M.oH (20 mL)
was !dd.d b Feipiht @l .opolyB.r 'nE copolymer was frlatd ard wlsncd wilt
CHrCI: (20 x 3), ic€tm. 120 x , atrd McOII (20 r 3), lrd dn.d uftt r $cuub
In rh. li@toE only wo !hpl6 hrw ba fdnd, wh.E .llyl ccn@n6harc b.en u$d to pDdnce copolymcs ofrllyl llcohol and .lhyl.ndpopyt.n. by in Ilcatalysl conbinins i.denyl rnd l)rcrdyl lis.rds and i Ticvelhyl iluDiniun
s6qDichlond. olid cablyst rrrr'
H.d wc Eporl dE coFlymaianion of c6yld sd rllyl co-morm.E (illyl
elhyl clb.r, .llyl bronidc) lo produe linar oopolymers using (PO,OM'PdM(Py) as
well 6 !$. f@ calalysls (PO, OM.)PdMc. In oE crsc, w. led rlyl cGmononds
92
whm the oolar ffincriomlily is ofi CH, soup !w!v liN thc nndiotrl group r otls
b aproE i.Gdbg FoFnics ol th. dDlling copoltn6 Th' ceDo|m6 {'llvl
dtyl erhcr Ind alltl bromide) s.ft d.gas*d In $Fe cvclcs l\a!uunhrtugen) Drior b
@ RaRsnbnv. Eillrs d. lhoq in Tablc 4 5
T.bk ir,s: C@olyhdiz:tion of cthvl* with allvl brmid' 'nd 'llvl 'tnvl
ctld
G.neEl colditiont: Ctnlvsl 20 psot Tol!@
AEEI= Allyl ethyl .thd, NS _ do1 dgnii.rnl
9l
Copoltmdr.ton ot Elhylo* drb A|lJl Etlttl Eth.r
.'ff ta I
s.b.m tt2: Copolyn.rizxion of.rhylerc end allyl .thyl cdEi
Copolynsiznion of dlyl cthyt ctlEr wnh .rhyld. qd Frforn€d lnder lh. llerrion MditioB 6 us.d for rlE honoFly@rittrion of .{hyl* lo codpoE l[.
A.@din8 lo lne Butls sbown in thc tdl€ th.E w6. Eguld ie|!e in % nol
inccrponlis of @!MoB ard r d€.t.e i! Dolcul& wi8!t .rd yicld of be
F.duc wniL im@ing th. @ldi@ ot th. @mffi This tFtd 3@s @ ss@h riu to nml co@hlior of Gm6@ an r r|{) mml inc6irg ih. cd
mnoftr @@n|t!Iron, a dop in % ml ifqpodtion is obscd along wilh nolculd
rcieln $ rcl d yicu TIE high6l im'po..!d btl *bit d sa 48 96 ml ai4 tlo
mol of allyl ethyl .ther qith M, 2 9 x lo1$ calculat.n bv 'H'NMR tFcIra Aftq '10
nml of .llyl.dryl crrq. funls a.lditid d@tuero lslt d i. ! deEls€d ticld of
copoltru $ w.ll a [email protected] of @II|@ro'
NMR 6ulE sow $!r th.E is d iFhdn [email protected] of slvl .rhvl .thq units
inro (hc D.in polycihyl.D. bek botc, LorFratioo of CH,4HCH2OEI in+hain u ls
i. polFhyld ir f!.th. oftrb.d by Ntu!@ r n & bv 2'NMR st d. (C!SY.
HMQC). Th. b chain ui.' cd b. 8.EnLd by I,2 d 2.1 i6!id of ctlr4lcHtoEtimo iPGOMc)PdCH:CH?P spei6 3 ob&.v.d in liL'lduE [& 91 -
el,rd",, - rx,Pd 9P rr x x
vP --l -x..---Pd,22.'f+Pd.'...'.'/x .-'.,' - - I "--r..".-"
Sc[.o. tl3: Copoly@irrli@ of .thyLt with .llvl .thvl clt r !d ttlvl bobiL'
ft. m.ch.nistic ehd. fd th. .oPolyo.iatio' oi.$vl.re shows thd tn. co'
mmodd ircoDoErion i o rh. loly.dylm b&Lbotu is bv 21 insti@ How'vd,
dcbil.d meh.nisli studi* d it p|@$,
t.3.,r NMRChrrrct.riatio! of Etbyldd EEcoporvidErhylcrc dd clyl cdryi etls copolvhci w.re chdc&nbd bt lH
'Dd rrc_
NMR sr.crFsopy, tlle utu.toraEd lnns tr (4HdHCH,P), CCH,CH'€HCH:P)
Th. oo'monom.r unil CcHcHrocH:cH, imorPoBdon w$ dclenircd bv H lnd rrc_
NMRsp.ctd llc!. r.sulls aF fuih{ @n,imcd bv assjg.ddll ofCOSY DEPTI35
.nd HMQC. Th. !.$Its e ffiai4d b.row
'H-r$a (cDct€Dcl, l2o qc, 4oo Mli?. t): (1.21, t) oclfi'cHr; {16, n).CHCHTOCH,CHT; (1.14, O {H.clirOCH1CH!: (1.52, q) O'CttCHt (a.93, d)
'CH:{HCH:B (5.08, d) lCHt=cHCH,Pi (5'l9 t) CH,'CE-C!I'CH:P: (5'86 s)
CH2=CH'CH2P.
rc-N\4R (CDCIICDCL l2O oC, 4OO MH4 6); (11,4) lCHrCHr
CCIICH1oCH,CHt; (14,2) FcHri (15 5) -OCH:'CHj; (230) PC|'CHCHITCH:P
121.6) C|j.CH'CH-CHCHTPi 132.!) PCg=CH{CBrn'CHrrl (134)
CHrCH-CH'CII:P: (34.4) P'CH:CH<H' (37.7) (PtCECIICH:CHfICH! (391)
(PCg1'CHCHflCItrOCIIlctIl; ('l0O) (PCHfCgCthCliilCH,oCtlCHt; (666)
o'cHlc8ri (7r'6) -'cHrocH?
,*rr(*"S.h.m. a 4: Copolynerianon ofcthvl* 'rd
alvl brooid'
CoDolyr.riatio qpdindts ofalyld. md lllvl bbnid. sd tle 6Ei.rl ou' using
lcrious @@oD.r cME rid. Hkhcsl % iMtpd.tid obw.d w.5 0,78% tr I tndol lllvl bMidc. Aft.r 15 mol. il siift d.o@dna
Two .xD.rinents t.E dmc usins ihc he &c. Pd(PGOM!) crlalvst wi$ 40
mnol of allyl olhyl cd.r ..d 15 mol oflllyl ttrdida at 80 "C, 50 ot lolu"'' 3 4 ddri
(50 p6i).thyl* PEsse fu 2 h It c& of .tlyl .thvl..ha, iMee inrvn b obw'd
rnd % incolpontioh n dcd.s. How*r, for allyl bodidc borh M, as well as %
ifo+.Etion in.g$. For 10 md t0 mol of dlyl banid., th€ copolyDcr y'.ld *,s
4.3.5 NMR Ch.r.ct ntrdotr of Eibylenc 3d Allyl Bro! de
Erhylcn. adt lllyl br.nid; coDolFcts w.t chdlclctiDd bv 'H atd 'rC_NI&
sp.ch$opy. fic un$o',ted lnib G ({H.CHCH?P), (aH:CH=CHCH:?) Thc co_
monmd unir {<HCHrBr) i.@ipoEtion *s dffihcd by rH and "C_}IMR sPef!.
The Esull. .ft smm.n&d below:
rH-NMR {cDctzcDc}, r20 !c, 400 r,fi4 6): {r.47, d) -cH'c}LB! 0.69 n)
'CHCH:BI (a97, d) 'CH'{HCH:P| (t4?, s) CH,'CH{HlCtlrP; (537 n);
CHI{HlCltlP.
'rc-Nr,,(R (cDclrcDo:, r2o 9c, aoo r!flra 0): Oa.o) P4Hr; O?.3) 'cHjcH{H};\221) PCH=CHCHrrCH]P| (26.8) CHTTCH,CILCH{FPi Q7 2)
Pc&*CH:Cn(CslBr)Ct{,P; {320) !CH-{A'CH,CHIPi 03 1) CgrcH{H'CHrPj
(11.8) P'CH:CIt{lt:i (379 CH,{H'Cg,Cr[Pj (395) cg'CHr& (40,4) -'cHcHlBr; (114.2) PcHrcH-*cH,r 02as) CHrlcH=cHCH,P; (1309)
CHjCH:CH=.CHCHTP; (131.8) CHrCn='CnClt?P; (139.6) PCE?'CH-CH!
The a$igmcuts of rlyl bbDid. ed lilyl .livl erhd s.c md. bt COSY_NMR
fFieuE: 4.3). P..grC''iCH,Br)CH,P b conchled io Pry7fH(CH,Br)CHlP The
obbiEd r.lu.s fros rH @d ':C-NMR !c @FFblc ro $. rE od rrC-NMR v.bB of
nod.l compounds r! shom in ol n41.
*f';:
Chrd4.l: N 4td.b rq mod.l conpoun& tCDCt., l]M EnFmoEt.
sd* rlpGbi.lE Det @.hon bclo*
Irrln a.2: |H-NMR (cxrtcDor l2orc) of .tbtld.hllyl b(sid.(l!) coDotF.
I.i .i
'11
i
neu..,3: COSY NMR (CDClrCDclr, l2O'C) oflihyla./.lM tr@i& ( B)
@tolvtu
98
L, --*)f!i 'UL
Flgrr. ,t.4r HMQC {CDCLcDClr, l20f) ot.lbyh.r'dlyl .thy and (A!E)
copolymd,
,@1*Htnzc'
Flgure 1.5. DEPTj3s (CDCI:CDCL, 120 'C) ol.drylelc/,nyl .i,\yl .tFt (aliE)
coporv6.r'
I
REFERENCES
1.
2
3.
\2.
EsrcD.lis, Migul, A., .l rr 6sun.n.ta4i6 20{'3, 22 !95
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Frdhlich. R.; Sons, H. O/s,,o'?r"lli.r' 2006, rJ, 196t. (b) Zlrlne, w i Sln w
H.i Teg, X.; G!o, T.iaE g, S ,Hto,PiCh. ,I J Mol cat /: ChenicoL
2006,l6J,159.
E1i^s,H C. ln tnhod!.tiu to Patt./ J.rh.d", VCH: w.inh.im, Gcmrnv,l
4. S!&r'bsg, Si OI(s.a M.; zws, L: zt^ai['g, k Lto Ch.kie
Sco n lI i n d ica, t995, 4 9, 639.
5. Don!fiy, M D.i Tru<teN, S.i Whir, P S.; Morkd, .L P.; Brooknaft, M
Organo netalli.t.z007. 5, 1261.
10.
Cml., M. P.; BumE C.T.; Idd.t\R.F. [email protected], 26,6750,
lz) Alr,H.4. C.a l. Ctem. Ra 2006,250,2.(h)^r,H.G.Dalb, rtunt 2005,
t21t.
vch, J ; Lict C. R.; Shd, Z: todtn,P,. F. Organouaalli.s ,001, 26.66N.
(r) Luo, S.; v.la, J.i |-i.t G. R.t !.tdtn, R. F- J An. Chfu. Soc ,001, 127,
8946 (b) vd8, W,i Shd, Z.; Iordan,R. F. J. An Cien. Soc.2001, I 29. 15450.
(!) lohnsn, L. Ki Kjlria4 C. M) Bt@nn,M. J. /n. Chn Soc. 1995, 117.
6ala O) Killie, C. M.; T.mpcl, D. J.; Jol'@, L. K.; B6olih.t! M. J ,ruCten. So.. t996, 118, I r66a lc) SDrll, B. L: Btu*hrn, M.; B€rc4 A. M. A
J Aa. Ct^ S@, 1994, u9.
Iouri, J. L; &sliwa, N.j Tod& V J.,1n, Chen. 3o..2002, 7, r24.
''C-NMR .Bi3M6t rotr polync6 e bsd d {a) &l@ Gall.nd, G.: d.
Sora, R. F.; SbloeMruld, R.; Nones,R. F. Ma.rcdottutes. 1999,32, 1620.
(b) Randatl, J. C.; Hsieh, E. T . .r, NMR atur Mo.rctual.cules: ^CS
Synqosin
Sdi.s 24tj Rrdrll, .t, C.; Ed., AocncD Chdi€l Sei.$ washin4or. D C.,
r98a; cbltr' 9. G) BEihid, E.;v6rb,1$. Carbon-|3 NMR Sp*toscw,
l( .d.; VCH: N.w Yods r9&7.
100
CONCLUSrcNAND
FUruREWORK
CONCLUSION AND FUTURE WORK
Ch'onim (l[) dpl.xca @Dl!ini4 difr.mt 3lbstitulcd 2{uhq!linyl-6-
iminoDyridine lisods luE ten ebjaEd b stdy erbyldc dismaizrim lnd
polyn.ianim. Polyinaiztion actids v.c p.rfm.d .r dificMl Ectio @ndirids
li*a DNE of edryleft, Enp.BsE, lnd @n6l$tion of crhyld..s '.ll.s rhc cec.ulysl modiied netn/.luninob. (MMAO). lilrd d.hibtoE ed r@riot
conditim have g@t innudc. on th. oullric lcrivity. tlis is aedding io th. mn!
objeciivc of pEenl wo*. Thc s.rcnl r..d fouowcd rg.lding this could b. dcpicied as
C-l < C-2 < c-3 < C-]|. fi.li8b.st ictility rhicv.d w..0.7 x 10" s PE Dol otcrh'ior c{ at l0 psi e rylene pressur., 1000 Al/Cr molir lio and 60'C. w. hnv. achi.led
inimsting r.sulls by fin. tunirg of !!tuctuc of crtalFl C4 oontaining 2,4,6-tin tlyl-
N-(116-{quinoxaliF3-yl)Dridin-2-y1).lhylid.nc)bondimine ti8,nd. Al 30 psi.lhylcne
prc$lE, PE 0divily ws 2 ?2 r 10" g nol ol Ci'h '. Thc lin.ar PE obtlined wd
chaaclenzd by DSC and IR. IrE DSC rBl}5b ior lE ssplcs suesested ! n€ltint
Thc pcllad'un (r) sll,sll cond .g nii.d <idDd lis:n& {sbltituGnphosphin6 md dilia) hft h.a utilizd ro in6tig.r. lhe olisomsizatio ofedyl@wtll MAo !s clHblysr Th. nslr wrlcd t .ting rhc lolyl lleqhi@ Iigrnd
cosllnl dd changing rh. subrituic! .nilir* o!&d ! siSrifimi ch.ng. in c.6ltric
.criviry. Adiviry inces.d in rhc ordcr ot c-r4: c-9 < c-8 < c,l1 < c-13 < c-to <
cl2. Ih. high.n activity &hi.y.d wls L6 x lo's molld| Iti for Cl! (vnicn h.s
chloF subslituenls 6 6. s.b lrd prs position), Ihis night b. du. ro d .letusithdnwin3 efi@t ofchlob groDps on .nilin cEltin! D .l*ton d€fici.i n bl cdrdrc lring in t noi€ el€clrophilic DcGl end thd nishl a*ibit nbna ctivily.
lvorcover, nDE bulky substitocn6 favor chrin $nsfcr reiction! Esulriag in oligoner
producl'or. A. DcEasing prc$ur ol alhylcDo rcsults in an i.cE,$ of &rivity Thc
sla33cEd snnade or rb. dilie nrdb8.n .nd cblob subslituqrs causs an el*tloD
wilhdEwd Aon tlc fthl cdtcr ircEring th. lcrivity $ illusfated by Newn!
TIE honop.lymdtzrion of crhyld hd @polyDdaton 6f ed'yltu virh
dill*nt Fhr cmoroM Ms inv.sdgarcd uling Pd(POOM€)M{Py) dd !.* nEPd{POOM.)M. €trlys. Th. @lE oblri*d by hooopolyndiztion of .rhyld
illusrcd ln. foD.lior of til@ potycrfiyl.nc vnn bw ftdlyl bo*h.s ar 50 psi
elhylde pEsrq 80 oC, fd 2h n. potycrhylft *6 prduc.d by pd(po
OMe)Mc{Py) in 1.22 s yicld md a nunb4 rlco8c doleular weish fM, 5 6 x r Or) w6calculabd fioh |H-NMR spocrra. Howav{, r nufrbtr avhC! dotcculli wcishi ro.polyethyla€ poduo.d by ?d(?O,OMc)M. {6 ? 8 x tor undd th. !!d. ftaction
corlihoB. In o& of $. c.pobDsiador of.dyld. witn dtyl .thyl aihd, rh. hisbesr
tn.oAoblion orio for.llyl.d!yl db.r &ni.\rd wc a 8 not % with,r, = 2.9r ld !t,(0 nnol of .o-oonomr unda dE m. E.ctid andirim s ued for dc bmo-polfoerialio of .ilyld., Fu atlyl bmid. high4l incdlonrjotr drio lcni*ed wis0?3 mol % .t 15 mol of the rcsDectiv. co-homner u'dq lhc s.me rcacrim
conditioB. By utilizins r bis-ne Pdcro-oMc)M. car,lyst fd dE oopolyd.rizrio! of.lhyl* w$ borh dyl crhyl efid sd .llyl bbhidc, d iEes of i&orDodtioD nriq,t/,6 ell rs rhc yi.ld v* obeftd. ('H and rrc) NMR E3ulrs lrot.d ihe
inmrpoatior of 6-mo!@d uia ino th. h!i! brchboft of potytthyl@. In ce otallyl elhyl.tlFr, L)C-NMR Es@06 w.c funhcr rlsigned by asisnDc. ofDEpTt35as w.ll as ty HMQC I. ce oI .llyl bMid!, 1he incdpo!.tion of thc co-horcDer
unns inb polycrhyl.D. v.! conitued by 1D-NMR aH, rrc) &d 2D-NMR (COSY).
wc h.!e achicvd sma tnhdng Etutll hy fin. tonins of cioDiuB dblysr. nEhiShd aoliviry w!. rchir!.n *n€n 2,4,6-Eidctiyl-N{l (6,(quinox.liD-3-yt)pFdi.e2
ylelhytidde)b€nzimino lisrnd w.s lsd lo sinlncBiz C4 c.ialyst, which is accddins to
thc mai. obj.divc oa pElenr sludy. Simihrly, in ce of pallodiun ra6lyrB, hiehei.ctivity for dn/.G oligondiario ws rchi.v.d for Cl2 colatFt vh.! md dd p@subdituled cblm milinc *c mplotrd $ lirrd. Pd(POOM.)M{Py) ablystsproducd copolyid oa.dryla. dd lyl .tnyl .dd .nd iltyl brmid..
Pd(Po-OMe)Me(Py) crldy.h an alF .oDobdcne cdryldc and allyl .lcohot. ]rEd.!il inwslisrtid of thi! sludy is in p@.$ IrE palladiuD (ll) c ilyslc cotuinins2,9ii@lhyl-1,10-phcdnth!li nd diil:E r subsrirub{t phdDhies sh@ld b.i.Bbgit.d lor.rhyl.n? ohStudiadon 6 mU s potFhzrion
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