Research Article Synthesis, Characterization, and Thermal ...

Hindawi Publishing CorporationJournal of ChemistryVolume 2013 Article ID 568195 12 pageshttpdxdoiorg1011552013568195

Research ArticleSynthesis Characterization and Thermal and AntimicrobialActivities of Some Novel Organotin(IV) Purine Base Complexes

Reena Jain1 Rajeev Singh2 and N K Kaushik3

1 Department of Chemistry Hindu College University of Delhi Delhi 110007 India2Department of Chemistry Atma Ram Sanatan Dharma College University of Delhi Delhi 110007 India3 Department of Chemistry University of Delhi Delhi 110007 India

Correspondence should be addressed to Rajeev Singh rajeevarsdduacin

Received 27 May 2013 Revised 4 August 2013 Accepted 7 August 2013

Academic Editor Sulekh Chandra

Copyright copy 2013 Reena Jain et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

A new series of organotin(IV) complexes with purine bases theophylline (HL1) and theobromine (L2) of the types R3Sn(L1)

R2Sn(L1)Cl R

3Sn(L2)Cl and R

2Sn(L2)Cl

2(R = C

6H5CH2ndash p-ClC

6H4CH2ndash) have been synthesized in anhydrous THF The

complexes were characterized by elemental analysis conductancemeasurements molecular weight determinations UV-vis IR 1H13CNMR andmass spectral studies Various kinetic and thermodynamic parameters of these complexes have also been determinedusing TGDTA technique The thermal decomposition techniques indicate the formation of SnO

2as a residue The results show

that the ligands act as bidentate forming a five-member chelate ring All the complexes are 1 1 metal-ligand complexes In order toassess their antimicrobial activity the ligands and their corresponding complexes have also been tested in vitro against bacteria (Ecoli S aureus and P pyocyanea) and fungi (Rhizopus oryzae and Aspergillus flavus) All the complexes exhibit remarkable activityand the results provide evidence that the studied complexes might indeed be a potential source of antimicrobial agents

1 Introduction

Organotin(IV) compounds are characterized by the presenceof at least one covalent carbon-organotin bond The com-pounds contain tin centres which are tetravalent and are clas-sified as mono- di- tri- and tetraorganotin(IV) dependingon the number of alkyl (R) or aryl (Ar) moieties Duringthe last 65 years the worldwide production of organotincompounds and their derivatives has increased considerablyowing to their activities as anticancer [1] antifouling [2ndash4] and bactericidal [5ndash9] fungicidal [7ndash13] antifertility [68 9] and antiviral agents [14] Since biocidal properties oforganotin(IV) compounds are dependent on both the organicgroup and the ligand attached to the tin [15 16] an interestingdevelopment is introducing ligands which are themselvesbioactive [15 17ndash19]

Compounds containing purine play a significant role inmany biological systems [20] where they exist in nucleicacids several vitamins coenzymes and antibiotics Theseprovide potential binding sites for metal ions and any

information on their coordinating properties is importantas a means of understanding the role of the metal ionin biological systems Theophylline (1 3-dimethylxanthine)and theobromine (3 7-dimethylxanthine) are referred toas purine bases and constitute an important class of anti-inflammatory agents [21]Theophylline has biological impor-tance as it is structurally related to nucleic acids components[22] and thus can be used as a drug for the treatmentof asthmatic bronchitis and chronic obstructive bronchitisunder a variety of brand names and as anticancer drugs

The interest inmetal complexes of theophylline and theo-bromine is stimulated by the fact that certain purine-metalcomplexes have been found to have therapeutic value asdiuretics [23] It is also important to study the mode ofbinding of the ligandwith themetal [24]Moreover the studyof the behavior of theophylline as a ligand can be useful forelucidating the metal and interligand interactions involvingthe purine bases of nucleic acids or their nucleosides as thetheophylline molecule can be considered as a model for thenucleoside guanosine In continuation of our previous work

2 Journal of Chemistry

N

N

C

C

O

O

NH

CH

N

5

43

2

16

78

9C

C

CH3

CH3

(a)

CH

N

N

C

C N

N

H5

43

2

16 7

89C

O

C

O

CH3

CH3

(b)

Figure 1 Structure of (a) theophylline and (b) theobromine ligands

here we present the synthesis mode of binding thermalstudies and antimicrobial properties of some organotin(IV)complexes with purine bases theophylline (Figure 1(a)) andtheobromine (Figure 1(b))

2 Experimental

21 PhysicalMeasurements All reagents used were AR gradeand the solvents were purified and dried by standard meth-ods and moisture was excluded from glass apparatus usingCaCl2drying tubes The elemental analysis was carried out

on an Elementar Analysensysteme GmbH Varion EL IIIGermany IR and far IR spectra were recorded on KBr andpolyethylene discs respectively using a Perkin Elmer Spec-trum 2000 FTIR spectrometer The 13C and 1HNMR spectrawere recorded in CDCl

3 respectively on a Bruker Spectro-

spin Advance 300 spectrometer Tetramethylsilane was usedas an internal reference for 1H NMR Varian Cary 100 UV-VIS spectrophotometer was used to record the electronicspectra of the compounds Conductance measurements werecarried out on Elico Conductivity Bridge (Type CM82T)and mass spectra were obtained using Jeol SX-102(FAB)mass spectrometer Thermal studies (TGDTA curves) wererecorded on a Rigaku Corporation Thermoflex PTC-10A instatic air at a heating rate of 10∘Cmin The Pt crucible wasused with alumina as the reference material Chlorine wasdetermined gravimetrically as silver chloride [25 26] Tinwasalso estimated gravimetrically as SnO

2[27]The antibacterial

activities were evaluated by the paper-disc plate method [28]and antifungal by agar plate technique [29]Molecularmassesof the complexes were determined by Cottrellrsquos method ofboiling point elevation [30]

22 Antimicrobial Activity

221 Antibacterial Activity For the evaluation of degreeof inhibitory effects on the growth of a wide spectrumof microorganisms antibacterial activity was performedagainst one Gram-positive (Staphylococcus aureus) and threeGram-negative (Escherichia coli Pseudomonas aeruginosaand Klebsiella pneumoniae) bacteria In order to compare theresults obtained the Imipenem was used as standard drug

Determination of the antibacterial activity was carried outby the paper-disc plate method [28] The compounds weredissolved in DMF at 500 and 1000 ppm concentrations TheWhatman no 1 papers with a diameter 5mm were soakedin these solutions These discs were placed on the appro-priate nutrient medium (05 peptone 015 yeast 015beef extract 035 sodium chloride and 013 KH

2PO4in

1000 cm3 distilled water which was autoclaved for 20min at15 psi before inoculation) previously seeded with organismsin Petri dishes and stored in an incubator at 28 plusmn 2∘C Theinhibition zone thus formed around each disc was measured(in mm) after 96 h

222 Antifungal Studies Bioefficacies of the synthesizedcompounds were checked in vitro The in vitro antifungalactivities of the ligands and their complexes were evalu-ated against two pathogenic fungi Rhizopus oryzae (causeszygomycosis) and Aspergillus flavus (causing aspergillosis oflungs) by the agar plate technique [29] In order to comparethe results obtained the Bavistin was used as standard drugThe compounds were directly mixed with the medium in001 and 01 (inmethanol) concentrationsThemediumwasthen poured into Petri plates and a small disc (07 cm) of thefungus culture was cut with a sterile cork borer and trans-ferred aseptically into the centre of a Petri dish containing themedium with a certain amount of the compound Suitablechecks were kept where the culture discs were grown underthe same conditions on PDA without the compound ThesePetri dishes were wrapped in polythene bags containing afew drops of alcohol and were placed in an incubator at 25plusmn 2∘C Controls were also run and three replicates were usedin each caseThe linear growth of the fungus was obtained bymeasuring the diameter of the fungal colony after four daysThe amount of growth inhibition in each of the replicate wascalculated by percentage inhibition = (119862minus119879)times100119862 where119862 is diameter of the fungus colony in the control plate after96 h and 119879 is diameter of the fungus colony in tested platesafter the same period

23 Preparation of Complexes (C6H5CH2)3SnCl (p-ClC

6H4sdot

CH2)3SnCl (C

6H5CH2)2SnCl2 and (p-ClC

6H5CH2)2SnCl2

were synthesized by the method given by Sisido et al[31] The organotin(IV) complexes of theophylline (HL1)

Journal of Chemistry 3

and theobromine (L2) were synthesized according to theprocedure reported by Bhatia et al [32]

A solution of theophylline (HL1 180 g 001mol) in 25mLTHF and 5 gNaOH was stirred for about 12 hrs at room tem-perature A solution of R

3SnCl or R

2SnCl2(001mol) in 25mL

THF was added to it and stirred for 4H at room temperatureThe contents were then filtered and the filtratewas reduced toone-fourth of its original volume The R

3SnL1 or R

2Sn(L1)Cl

complexes precipitated out on adding petroleum ether andwere recrystallised from acetone Theobromine complexeswere synthesized by simply adding a solution of R

3SnCl

or R2SnCl2(001mol) in 25mL THF to a suspension of

theobromine (L2 180 g 001mol) in 25mL THF and stirredfor 3 hours at room temperature The contents were filteredand volume was reduced to one-fourth of its original volumeThe R

3SnL2(Cl) or R

2Sn(L2)Cl

2complexes precipitated out

on addition of petroleum ether and were recrystallised fromacetone

3 Results and Discussion

Elemental analyses reveal that the complexes are of goodpurity and are yellow in colourThe complexes were found tobe soluble in acetonitrile THF DMSO acetone and CHCl

3

The complexes decomposed before melting The analyticaldata of the complexes along with their decomposition tem-perature is given in Table 1 From the analytical data it is clearthat organotin(IV) derivatives react with these ligands in1 1 molar proportions Conductancemeasurements for thesecomplexes in 10minus2M nitrobenzene solution are in the rangeof 012ndash040 ohmminus1 cm2molminus1 indicating that the complexesare nonelectrolytes

31 Infrared Studies In case of theophylline complexes theligand can chelate with the metal ion either through C(6)carbonyl and N(7) or through N(7) alone [24 32 33] In thepresent case the ](C=O) stretching frequency for free ligandwas observed at 1720 and 1660 cmminus1 On complexation thepeaks merged and appeared at ca 1700 cmminus1 However thisshift cannot be attributed to the interaction of carbonyl atC(6) with Sn(IV) since the electronic spectra of these com-plexes rules out this possibility Further the disappearanceof the band at 3200 cmminus1 due to ](NndashH) stretching in thecomplexes indicate that the ligand is linked to Sn(IV) throughthe deprotonation of N(7)

In case of free theobromine the ](C=O) stretching fre-quency appears at 1700 and 1665 cmminus1 and remains unalteredon complexation However the ](C=N) + ](C=C) stretchingfrequency is shifted from 1595 and 1550 cmminus1 in free theo-bromine to ca 1580 and 1530 cmminus1 in complexes indicatingthat the theobromine is linked to Sn(IV) through N(9) [34]

32 Electronic Spectra In the electronic spectra of theo-phylline and theobromine the band corresponding to 120587 rarr120587lowast transition of the carbonyl group at 270 nm (log120576 345) and

272 nm (log120576 35) respectively almost remained unperturbed

on complexation confirming the noninvolvement of the car-bonyl group of these ligands in complexation [32] Additionalpeaks at sim210 nm and sim250 nm corresponding to the phenylring of R moiety are observed in case of the UV spectrumof metal complexes In addition to this the ligand rarr metalcharge transfer band is observed in the region 320ndash340 nm(log 120576 sim 42) in the complexes

33 1H and 13C NMR Studies The 1H NMR data of thecomplexes are tabulated in Tables 2 and 3 The peaksundergo a slight downfield shift on complexation due tothe change in the electronic environment of the ligand Intheophylline the broad peak due to ndashNndashH (120575 104) disappearson complexation confirming that the complexation involvesthe replacement of hydrogen atom in ndashNndashHndash group In theo-bromine the peak corresponding to H-8 (120575 71) undergoessignificant downfield shift on complexation confirming theinvolvement ofN-9 in complexation [35] 13CNMRdata havebeen recorded for both the ligands and their correspondingorganotin(IV) complexes and these spectra also support theauthenticity of the proposed structures (C

6H5CH2)3Sn(L1)

13CNMR ppm theophyllinato C(2) 1558 C(3) 1495 C(5)1073 C(6) 1623 C(8) 1411 1-Me 284 3-Me 301 SnndashCH2 1787 aromatic 1418 1306 1288 1317 1279 1316

(C6H5CH2)3Sn(L2)Cl theobromine C(2) 1511 C(4) 1495

C(5) 1063 C(6) 1612 C(8) 1365 3-Me 291 7-Me 284 SnndashCH2 1956 aromatic 1428 1316 1298 1327 1289 1326

34 Mass Studies The fragmentation pattern of the com-plexes has been analysed on the basis of mass spectra TheRSn+ R+ and Sn+ ions dominate the mass spectra Thecarbonium ion R+ constitutes the base peak in the massspectra of all the complexes Schemes 1 and 2 representthe fragmentation pattern for theophylline and theobrominemoieties respectively in the organotin(IV) complexes

35 Thermal Studies Thermal studies have been carriedout for all the complexes The thermogravimetric (TG)studies reveal that only two of the prepared complexes(C6H5CH2)3Sn(L1) and (p-ClC

6H4CH2)3Sn(L1) undergo

decomposition in two steps whereas the rest undergo decom-position in three stepsThe first step (423ndash673K) involves theloss of R groups the second step corresponds to the loss ofchlorine atom(s) and the final step involves the formationof SnO

2 The mass loss data is given in Table 4 The DTA

curves reveal that all the decomposition steps except the stepcorresponding to the formation of SnO

2 are exothermic in

nature The last step corresponding to the formation of SnO2

is endothermic in natureThe order (119899) and activation energy (119864

119886) have been

elucidated for the various steps using Coats-Redfern [36]as well as Horowitz-Metzger [37] methods The values ofactivation energy and entropy of the reaction have beencalculated using both methods and found to be in closeagreement The order of reaction in each case is one ΔH(enthalpy of reaction) have been calculated using the TG [38]andDTA curves respectively [39 40]The kinetic parameters


Table1Ph

ysicalcharacteris

ticsa

ndanalyticaldataof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Empiric

alform

ula

MolW

tfoun

d(cal)

Decptemp(∘C)Λ119887(Cminus15

9times10minus2M)

Foun

d(cal)

SnCl

NC

H(C

6H5C

H2)

3Sn(L1)

C 28H

28N

4SnO

257076

(57124)

210

021

2019

(2077)

mdash96

1(98

0)5864(5887)

461

(494)

(p-C

lC6H

4CH

2)3Sn(L1)

C 28H

25N

4SnO

2Cl 3

67321

(67398)

170

019

1705

(176

1)1522(1569)

798(831

)4962(498

9)321

(373)

(C6H

5CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

51491

(51536)

240

024

2262(2303)

629

(684)

1038(1087)

4869(4894)

392

(410

)(p-C

lC6H

4CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

58261

(58385)

210

039

2006(2032)

1768

(1811)

926(959)

4299(4320)

302

(328)

(C6H

5CH

2)3Sn(L2)C

lC 2

8H29N

4SnO

2Cl

60681

(60750)

200

021

1916

(1953

)534

(580)

906(922)

5501(5535

)451

(481)

(p-C

lC6H

4CH

2)3Sn(L2)C

lC 2

8H26N

4SnO

2Cl 4

7092

9(71024)

150

029

1621(1671)

1931

(1985)

762(788)

4711

(4735)

329

(369)

(C6H

5CH

2)2Sn(L2)C

l 2C 2

1H22N

4SnO

2Cl 2

5510

0(55162)

220

030

2112

(215

1)1221(1278)

998(1015)

4554(4572)

365

(402)

(p-C

lC6H

4CH

2)2Sn(L2)C

l 2C 2

1H20N

4SnO

2Cl 4

6197

9(62011)

200

032

1869(19

14)

2219

(2273)

889

(903)

4021(40

67)

302

(325)


Table2

1 Hand

13CNMRdata(120575

ppm)o

ftheop

hylline

complexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theoph

yllin

emoiety

ArndashH

ndashCH

2ndashH-8

ndashCH

3atN-3

ndashCH

3atN-1

ndashNHndash

Theoph

yllin

e(HL1)

mdashmdash

75-76(d1H

)36-37(s3H)

32(s3H)

104ndash106(br2

H)

(C6H

5CH

2)3Sn(L1)

79ndash81(m

15H

)36-37(s6H)

77-78(d1H

)39-40(s3H)

33(s3H)

mdash1787

(p-C

lC6H

4CH

2)3Sn(L1)

80ndash

82(m

12H

)39(s6H)

76-77(d1H

)41-4

2(s3H)

34(s3H)

mdash2401

(C6H

5CH

2)2Sn(L1)C

l79

-80(m

10H

)38(s4H)

75-76(d1H

)40-41(s3

H)

33-34(s3H)

mdash1721

(p-C

lC6H

4CH

2)2Sn(L1)C

l80-81(m8H)

37-38(s4H)

77-78(d1H

)40(s3H)

34-35(s3H)

mdash2350


Table3

1 Hand

13CNMRdata(120575

ppm)o

ftheob

rominec

omplexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theobrom

inem

oiety

ArndashH

ndashCH

2ndashndashC

H3atN-3

ndashCH

3atN-2

H-8

ndashNHndash

Theobrom

ine(L2)

mdashmdash

33(s3H)

35(s3H)

71(s1H)

130ndash132(br1H

)(C

6H5C

H2)

3Sn(L2)C

l70

ndash74(m

15H

)38-39(s6H)

34-35(s3H)

36-37(s3H)

77(s1H)

132ndash134(br1H

)1956

(p-C

lC6H

4CH

2)3Sn(L2)C

l71ndash73(m

12H

)39(s6H)

33-34(s3H)

36-37(s3H)

76(s1H)

134ndash136(br1H

)2534

(C6H

5CH

2)2Sn(L2)C

l 270

ndash73(m

10H

)39-40(s4H)

34(s3H)

37(s3H)

75(s1H)

133ndash135(br1H

)1834

(p-C

lC6H

4CH

2)2Sn(L2)C

l 271ndash73(m

8H)

38(s4H)

33-34(s3H)

36(s3H)

78(s1H)

133ndash136(br1H

)2366


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905

Scheme 1 Fragmentation pattern for theophylline complexes


+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180

Scheme 2 Fragmentation pattern for theobromine complexes


Table 4 Phenomenological data for the thermal decomposition of the complexes

Complex Step number TG plateaux (K) Mass loss Nature of lossObserved Calc

(C6H5CH2)3Sn(L1) I 483ndash673 460 4786 Loss of 3 benzyl groups

II 893ndash1003 720 7373 Formation of SnO2

(p-ClC6H4CH2)3Sn(L1) I 443ndash633 550 5580 Loss of 3 p-chlorobenzyl groups


(C6H5CH2)2Sn(L1)Cl

I 513ndash663 347 3536 Loss of 2 benzyl groupsII 703ndash773 420 4220 Loss of chlorine atomIII 893ndash973 694 7088 Formation of SnO2

(p-ClC6H4CH2)2Sn(L1)Cl

I 483ndash673 420 4294 Loss of 2 p-chlorobenzyl groupsII 723ndash793 470 4898 Loss of chlorine atomIII 873ndash973 735 7429 Formation of SnO2

(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2

I 493ndash653 320 3304 Loss of 2 benzyl groupsII 703ndash773 450 4582 Loss of chlorine atomsIII 873ndash993 710 7279 Formation of SnO2

(p-ClC6H4CH2)2Sn(L2)Cl2

I 473ndash653 400 4043 Loss of 2 p-chlorobenzyl groupsII 723ndash793 500 5180 Loss of chlorine atomsIII 873ndash973 750 7580 Formation of SnO2

for the thermal decomposition of the complexes are given inTable 5

On the basis of the above data it can be concludedthat the complexes with R = p-ClC

6H4CH2ndash have lower 119864

119886

value for step 1 as compared to the complexes with the samenumber of R groups but R = C

6H5CH2ndash because the electron

withdrawing effect of chlorine makes the RndashSn bond weakerand facilitates its thermal degradation Moreover tri(p-chlorobenzyl)tin derivative has the least activation energy forthe first step due to the greater steric hindrance

36 In Vitro Antibacterial Studies Themetal complexes werescreened versus Ecoli S aureus and P pyocyanea bacterialstrains using the respective ligands as the standard forcomparing the activities The samples were screened at threedifferent concentrations (25 50 and 100 120583g cmminus3) in DMFThe inhibitory power of the metal complexes was observedto be greater than that of the control The general orderof activity versus the three microorganisms is Saureus gt Ppyocyanea gt EcoliThe data is presented in Table 6

37 Antifungal Studies The results reported in Table 7 revealthat the organotin complexes with these ligands are muchmore active than the parent ligand against the same microor-ganisms With increase in concentration of the compoundsthere occurs increase in percentage of inhibition Higherconcentration proves inhibitory for fungal growth

Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2

On the basis of spectral evidence Figure 2 representingcoordination has been prepared for one of the complexessynthesized

Conflict of Interests

The authors declare that they have no conflict of interests


Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm

olminus1Δ119878(JKminus

1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226


Table 6 Antibacterial activity of theophylline and theobromine complexes

CompoundDiameter of inhibition zone (mm) after 24 hr

Escherichia coli (minus) Pseudomonas aeruginosa (minus) Klebsiella pneumonia (minus) Staphylococcus aureus (+)500 1000 500 1000 500 1000 500 1000

HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13

Table 7 Antifungal activity of theophylline and theobromine complexes

CompoundAverage inhibition after 96H

Rhizopus oryzae Aspergillus flavusConc (001) Conc (01) Conc (001) Conc (01)

HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L

1)Cl 51 59 65 72Bavistin 82 96 84 98L2 36 48 42 54(C6H5CH2)3Sn(L

2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References

[1] P M Samuel D D Vos D Raveendra J A R P Sarma andS Roy ldquo3-D QSAR studies on new dibenzyltin(IV) anticanceragents by comparative molecular field analysis (CoMFA)rdquoBioorganic and Medicinal Chemistry Letters vol 12 no 1 pp61ndash64 2002

[2] R Singh P Chaudhary and N K Kaushik ldquoA review organ-otin compounds in corrosion inhibitionrdquo Reviews in InorganicChemistry vol 30 no 4 pp 275ndash294 2010

[3] D C Cinito Roberto and D C Giorgio Acquo Aria vol 9 p993 1993 Chemical Abstracts vol 120 Article ID 156632 1994

[4] A G Davies Organotin Chemistry Wiley VCH WeinheimGermany 2nd edition 2004

[5] M Ashfaq M I Khan M Kaleem Baloch and A Malik ldquoBio-logically potent organotin(IV) complexes of 2-maleimidoaceticacidrdquo Journal of Organometallic Chemistry vol 689 no 1 pp238ndash245 2004

[6] A Bacchi A Bonardi M Carcelli et al ldquoOrganotin com-plexes with pyrrole-25-dicarboxaldehyde bis(acylhydrazones)Synthesis structure antimicrobial activity and genotoxicityrdquoJournal of Inorganic Biochemistry vol 69 no 1-2 pp 101ndash1121998

[7] R V Singh P Chaudhary K Poonia and S ChauhanldquoMicrowave-assisted synthesis characterization and biologicalscreening of nitrogen-sulphur and nitrogen-oxygen donor lig-ands and their organotin(IV) complexesrdquo Spectrochimica ActaPart A vol 70 no 3 pp 587ndash594 2008

[8] R V Singh P Chaudhary S Chauhan and M SwamildquoMicrowave-assisted synthesis characterization and biologicalactivities of organotin (IV) complexes with some thio Schiffbasesrdquo Spectrochimica Acta Part A vol 72 no 2 pp 260ndash2682009

[9] P Chaudhary M Swami D K Sharma and R V SinghldquoEcofriendly synthesis antimicrobial and antlspermatogenkactivity of triorganotin(IV) complexes with 41015840-nitrobenzanilidesemlcarbazone and 41015840-nitrobezanilide ThiosemicarbazonerdquoApplied Organometallic Chemistry vol 23 no 4 pp 140ndash1492009

[10] R Singh and N K Kaushik ldquoOrganotin(IV) complexes of thio-hydrazides and thiodiamines synthesis spectral and thermalstudiesrdquo Spectrochimica Acta Part A vol 65 no 3-4 pp 950ndash954 2006

[11] R Singh and N K Kaushik ldquoSynthesis spectral thermal andanti-fungal studies of organotin(IV) thiohydrazone complexesrdquoSpectrochimica Acta Part A vol 72 no 4 pp 691ndash696 2009


[12] R Singh and N K Kaushik ldquoSpectral and thermal studieswith anti-fungal aspects of some organotin(IV) complexeswith nitrogen and sulphur donor ligands derived from 2-phenylethylaminerdquo Spectrochimica Acta Part A vol 71 no 2pp 669ndash675 2008

[13] A Bacchi M Carcelli P Pelagatti et al ldquoAntimicrobial andmutagenic properties of organotin(IV) complexes with isatinand N-alkylisatin bisthiocarbonohydrazonesrdquo Journal of Inor-ganic Biochemistry vol 99 no 2 pp 397ndash408 2005

[14] M Nath and S Goyal ldquoSpectral studies and bactericidal fungi-cidal insecticidal and parasitological activities of organotin(IV)complexes of Thio Schiff bases having no donor atomsrdquoMetal-Based Drugs vol 2 pp 297ndash309 1995

[15] C Pellerito L Nagy L Pellerito and A Szorcsik ldquoBiologicalactivity studies on organotin(IV)119899+ complexes and parent com-poundsrdquo Journal of Organometallic Chemistry vol 691 no 8 pp1733ndash1747 2006

[16] X Song A Zapata and G Eng ldquoOrganotins and quantitative-structure activityproperty relationshipsrdquo Journal of Organo-metallic Chemistry vol 691 no 8 pp 1756ndash1760 2006

[17] L Pellerito and L Nagy ldquoOrganotin(IV)119899+ complexes formedwith biologically active ligands equilibrium and structuralstudies and some biological aspectsrdquo Coordination ChemistryReviews vol 224 pp 111ndash150 2002

[18] E Katsoulakou M Tiliakos G Papaefstathiou et alldquoDiorganotin(IV) complexes of dipeptides containing the120572-aminoisobutyryl residue (Aib) preparation structuralcharacterization antibacterial and antiproliferative activitiesof [(n-Bu)

2Sn(H-1L)] (LH = H-Aib-L-Leu-OH H-Aib-L-Ala-

OH)rdquo Journal of Inorganic Biochemistry vol 102 no 7 pp1397ndash1405 2008

[19] MNath S Pokharia X Song et al ldquoNew organotin(IV) deriva-tives of dipeptides as models for metal-protein interactions invitro anti-tumour activityrdquo Applied Organometallic Chemistryvol 17 pp 305ndash314 2003

[20] F Hueso N A Illan M N Moreno J M Martınez and M JRamırez ldquoSynthesis and spectroscopic studies on the new Schiffbase derived from the 1 2 condensation of 26-diformyl-4-methylphenol with 5-aminouracil (BDF5AU) and its transitionmetal complexes Influence on biologically active peptides-regulating aminopeptidasesrdquo Journal of Inorganic Biochemistryvol 94 pp 326ndash334 2003

[21] S S Marwaha J Kaur and G S Sodhi ldquoStructure determina-tion and anti-inflammatory activity of some purine complexesrdquoMetal-Based Drugs vol 2 no 1 pp 13ndash17 1995

[22] S Nafisi A S Sadjadi S S Zadeh and M Damerchelli ldquoInter-action of metal ions with caffeine and theophylline stabilityand structural featuresrdquo Journal of Biomolecular Structure andDynamics vol 21 no 2 pp 289ndash295 2003

[23] J Kaur and G S Sodhi ldquoDiuretic activity of organomercury(II) complexes of theophylline and theobrominerdquo Journal ofInorganic Biochemistry vol 48 no 4 pp 305ndash410 1992

[24] S Nafisi D S Shamloo N Mohajerani and A Omidi ldquoAcomparative study of caffeine and theophylline binding toMg(II) and Ca(II) ions studied by FTIR and UV spectroscopicmethodsrdquo Journal of Molecular Structure vol 608 no 1 pp 1ndash72002

[25] A I Vogel A Textbook of Quantitative Inorganic AnalysisLongmans Green amp Co London UK 4th edition 1985

[26] A I Vogel Elementary Practical Organic Chemistry Part 3Longmans Group London UK 1971

[27] R C Poller The Chemistry of Organotin Compounds vol 6Logos Press London UK 1970

[28] H HThornberry ldquoA paper-disk plate method for the quantita-tive evaluation of fungicides and bactericidesrdquo Phytopathologyvol 40 pp 419ndash429 1950

[29] J G Horsfall ldquoQuantitative bioassay of fungicides in thelaboratoryrdquoTheBotanical Review vol 11 no 7 pp 357ndash397 1945

[30] N Kundu and S K Jain Physical Chemistry S ChandampCo LtdIndia 1984

[31] K Sisido Y Takeda and Z Kinugawa ldquoDirect synthesisof organotin compoundsmdashI Di- and tribenzyltin chloridesrdquoJournal of the American Chemical Society vol 83 no 3 pp 538ndash541 1961

[32] S Bhatia N K Kaushik and G S Sodhi ldquoStudies onorganomercury(II) complexes of isoniazidrdquo Journal of ChemicalResearch vol 6 pp 181ndash186 1987

[33] A R Norris R Kumar E Buncel and A L Beauchamp ldquoMetalion-biomolecule interactionsmdash5 synthesis and spectroscopicproperties of methylmercury (II) and mercury (II) complexesof theophyllinerdquo Journal of Inorganic Biochemistry vol 21 pp277ndash286 1984

[34] W J Birdsall and D L Taylor ldquoPreparation of copper(II) andzinc(II) halide and primary amine complexes of theobrominerdquoPolyhedron vol 8 no 21 pp 2593ndash2597 1989

[35] J Browning P L Goggin R J Goodfellow N W HurstL G Mallinson and M Murray ldquoPreparation and vibra-tional spectra of tetra-n-propylammonium carbonyldichloro-organoplatinate(II) salts and a comparison of their carbon-13and platinum-195 nuclear magnetic resonance properties withthose of organomercury compoundsrdquo Journal of the ChemicalSociety Dalton Transactions no 7 pp 872ndash876 1978

[36] A W Coats and J P Redfern ldquoKinetic parameters fromthermogravimetric datardquo Nature vol 201 no 4914 pp 68ndash691964

[37] HHHorowitz andGMetzger ldquoAnewanalysis of thermogravi-metric tracesrdquo Analytical Chemistry vol 35 no 10 pp 1464ndash1468 1963

[38] J Zsako ldquoKinetic analysis of thermogravimetric datardquo Journalof Physical Chemistry vol 72 no 7 pp 2406ndash2411 1968

[39] J H Sharp and S A Wentworth ldquoKinetic analysis of thermo-gravimetric datardquoAnalytical Chemistry vol 41 no 14 pp 2060ndash2062 1969

[40] W W Wendlandt Thermal Methods of Analysis John Wiley ampSons New York NY USA 2nd edition 1974

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


N

N

C

C

O

O

NH

CH

N

5

43

2

16

78

9C

C

CH3

CH3

(a)

CH

N

N

C

C N

N

H5

43

2

16 7

89C

O

C

O

CH3

CH3

(b)

Figure 1 Structure of (a) theophylline and (b) theobromine ligands

here we present the synthesis mode of binding thermalstudies and antimicrobial properties of some organotin(IV)complexes with purine bases theophylline (Figure 1(a)) andtheobromine (Figure 1(b))

2 Experimental

21 PhysicalMeasurements All reagents used were AR gradeand the solvents were purified and dried by standard meth-ods and moisture was excluded from glass apparatus usingCaCl2drying tubes The elemental analysis was carried out

on an Elementar Analysensysteme GmbH Varion EL IIIGermany IR and far IR spectra were recorded on KBr andpolyethylene discs respectively using a Perkin Elmer Spec-trum 2000 FTIR spectrometer The 13C and 1HNMR spectrawere recorded in CDCl

3 respectively on a Bruker Spectro-

spin Advance 300 spectrometer Tetramethylsilane was usedas an internal reference for 1H NMR Varian Cary 100 UV-VIS spectrophotometer was used to record the electronicspectra of the compounds Conductance measurements werecarried out on Elico Conductivity Bridge (Type CM82T)and mass spectra were obtained using Jeol SX-102(FAB)mass spectrometer Thermal studies (TGDTA curves) wererecorded on a Rigaku Corporation Thermoflex PTC-10A instatic air at a heating rate of 10∘Cmin The Pt crucible wasused with alumina as the reference material Chlorine wasdetermined gravimetrically as silver chloride [25 26] Tinwasalso estimated gravimetrically as SnO

2[27]The antibacterial

activities were evaluated by the paper-disc plate method [28]and antifungal by agar plate technique [29]Molecularmassesof the complexes were determined by Cottrellrsquos method ofboiling point elevation [30]

22 Antimicrobial Activity

221 Antibacterial Activity For the evaluation of degreeof inhibitory effects on the growth of a wide spectrumof microorganisms antibacterial activity was performedagainst one Gram-positive (Staphylococcus aureus) and threeGram-negative (Escherichia coli Pseudomonas aeruginosaand Klebsiella pneumoniae) bacteria In order to compare theresults obtained the Imipenem was used as standard drug

Determination of the antibacterial activity was carried outby the paper-disc plate method [28] The compounds weredissolved in DMF at 500 and 1000 ppm concentrations TheWhatman no 1 papers with a diameter 5mm were soakedin these solutions These discs were placed on the appro-priate nutrient medium (05 peptone 015 yeast 015beef extract 035 sodium chloride and 013 KH

2PO4in

1000 cm3 distilled water which was autoclaved for 20min at15 psi before inoculation) previously seeded with organismsin Petri dishes and stored in an incubator at 28 plusmn 2∘C Theinhibition zone thus formed around each disc was measured(in mm) after 96 h

222 Antifungal Studies Bioefficacies of the synthesizedcompounds were checked in vitro The in vitro antifungalactivities of the ligands and their complexes were evalu-ated against two pathogenic fungi Rhizopus oryzae (causeszygomycosis) and Aspergillus flavus (causing aspergillosis oflungs) by the agar plate technique [29] In order to comparethe results obtained the Bavistin was used as standard drugThe compounds were directly mixed with the medium in001 and 01 (inmethanol) concentrationsThemediumwasthen poured into Petri plates and a small disc (07 cm) of thefungus culture was cut with a sterile cork borer and trans-ferred aseptically into the centre of a Petri dish containing themedium with a certain amount of the compound Suitablechecks were kept where the culture discs were grown underthe same conditions on PDA without the compound ThesePetri dishes were wrapped in polythene bags containing afew drops of alcohol and were placed in an incubator at 25plusmn 2∘C Controls were also run and three replicates were usedin each caseThe linear growth of the fungus was obtained bymeasuring the diameter of the fungal colony after four daysThe amount of growth inhibition in each of the replicate wascalculated by percentage inhibition = (119862minus119879)times100119862 where119862 is diameter of the fungus colony in the control plate after96 h and 119879 is diameter of the fungus colony in tested platesafter the same period

23 Preparation of Complexes (C6H5CH2)3SnCl (p-ClC

6H4sdot

CH2)3SnCl (C

6H5CH2)2SnCl2 and (p-ClC

6H5CH2)2SnCl2

were synthesized by the method given by Sisido et al[31] The organotin(IV) complexes of theophylline (HL1)




3SnCl or R



3SnL1 or R

2Sn(L1)Cl


3SnCl



3SnL2(Cl) or R

2Sn(L2)Cl





3








6H5CH2)3Sn(L1)










2 are exothermic in



119886) have been



Table1Ph

ysicalcharacteris

ticsa

ndanalyticaldataof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Empiric

alform

ula

MolW

tfoun

d(cal)


9times10minus2M)

Foun

d(cal)

SnCl

NC

H(C

6H5C

H2)

3Sn(L1)

C 28H

28N

4SnO

257076

(57124)

210

021

2019

(2077)

mdash96

1(98

0)5864(5887)

461

(494)

(p-C

lC6H

4CH

2)3Sn(L1)

C 28H

25N

4SnO

2Cl 3

67321

(67398)

170

019

1705

(176

1)1522(1569)

798(831

)4962(498

9)321

(373)

(C6H

5CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

51491

(51536)

240

024

2262(2303)

629

(684)

1038(1087)

4869(4894)

392

(410

)(p-C

lC6H

4CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

58261

(58385)

210

039

2006(2032)

1768

(1811)

926(959)

4299(4320)

302

(328)

(C6H

5CH

2)3Sn(L2)C

lC 2

8H29N

4SnO

2Cl

60681

(60750)

200

021

1916

(1953

)534

(580)

906(922)

5501(5535

)451

(481)

(p-C

lC6H

4CH

2)3Sn(L2)C

lC 2

8H26N

4SnO

2Cl 4

7092

9(71024)

150

029

1621(1671)

1931

(1985)

762(788)

4711

(4735)

329

(369)

(C6H

5CH

2)2Sn(L2)C

l 2C 2

1H22N

4SnO

2Cl 2

5510

0(55162)

220

030

2112

(215

1)1221(1278)

998(1015)

4554(4572)

365

(402)

(p-C

lC6H

4CH

2)2Sn(L2)C

l 2C 2

1H20N

4SnO

2Cl 4

6197

9(62011)

200

032

1869(19

14)

2219

(2273)

889

(903)

4021(40

67)

302

(325)


Table2

1 Hand

13CNMRdata(120575

ppm)o

ftheop

hylline

complexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theoph

yllin

emoiety

ArndashH

ndashCH

2ndashH-8

ndashCH

3atN-3

ndashCH

3atN-1

ndashNHndash

Theoph

yllin

e(HL1)

mdashmdash

75-76(d1H

)36-37(s3H)

32(s3H)

104ndash106(br2

H)

(C6H

5CH

2)3Sn(L1)

79ndash81(m

15H

)36-37(s6H)

77-78(d1H

)39-40(s3H)

33(s3H)

mdash1787

(p-C

lC6H

4CH

2)3Sn(L1)

80ndash

82(m

12H

)39(s6H)

76-77(d1H

)41-4

2(s3H)

34(s3H)

mdash2401

(C6H

5CH

2)2Sn(L1)C

l79

-80(m

10H

)38(s4H)

75-76(d1H

)40-41(s3

H)

33-34(s3H)

mdash1721

(p-C

lC6H

4CH

2)2Sn(L1)C

l80-81(m8H)

37-38(s4H)

77-78(d1H

)40(s3H)

34-35(s3H)

mdash2350


Table3

1 Hand

13CNMRdata(120575

ppm)o

ftheob

rominec

omplexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theobrom

inem

oiety

ArndashH

ndashCH

2ndashndashC

H3atN-3

ndashCH

3atN-2

H-8

ndashNHndash

Theobrom

ine(L2)

mdashmdash

33(s3H)

35(s3H)

71(s1H)

130ndash132(br1H

)(C

6H5C

H2)

3Sn(L2)C

l70

ndash74(m

15H

)38-39(s6H)

34-35(s3H)

36-37(s3H)

77(s1H)

132ndash134(br1H

)1956

(p-C

lC6H

4CH

2)3Sn(L2)C

l71ndash73(m

12H

)39(s6H)

33-34(s3H)

36-37(s3H)

76(s1H)

134ndash136(br1H

)2534

(C6H

5CH

2)2Sn(L2)C

l 270

ndash73(m

10H

)39-40(s4H)

34(s3H)

37(s3H)

75(s1H)

133ndash135(br1H

)1834

(p-C

lC6H

4CH

2)2Sn(L2)C

l 271ndash73(m

8H)

38(s4H)

33-34(s3H)

36(s3H)

78(s1H)

133ndash136(br1H

)2366


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905



+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




3SnCl or R



3SnL1 or R

2Sn(L1)Cl


3SnCl



3SnL2(Cl) or R

2Sn(L2)Cl





3








6H5CH2)3Sn(L1)










2 are exothermic in



119886) have been



Table1Ph

ysicalcharacteris

ticsa

ndanalyticaldataof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Empiric

alform

ula

MolW

tfoun

d(cal)


9times10minus2M)

Foun

d(cal)

SnCl

NC

H(C

6H5C

H2)

3Sn(L1)

C 28H

28N

4SnO

257076

(57124)

210

021

2019

(2077)

mdash96

1(98

0)5864(5887)

461

(494)

(p-C

lC6H

4CH

2)3Sn(L1)

C 28H

25N

4SnO

2Cl 3

67321

(67398)

170

019

1705

(176

1)1522(1569)

798(831

)4962(498

9)321

(373)

(C6H

5CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

51491

(51536)

240

024

2262(2303)

629

(684)

1038(1087)

4869(4894)

392

(410

)(p-C

lC6H

4CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

58261

(58385)

210

039

2006(2032)

1768

(1811)

926(959)

4299(4320)

302

(328)

(C6H

5CH

2)3Sn(L2)C

lC 2

8H29N

4SnO

2Cl

60681

(60750)

200

021

1916

(1953

)534

(580)

906(922)

5501(5535

)451

(481)

(p-C

lC6H

4CH

2)3Sn(L2)C

lC 2

8H26N

4SnO

2Cl 4

7092

9(71024)

150

029

1621(1671)

1931

(1985)

762(788)

4711

(4735)

329

(369)

(C6H

5CH

2)2Sn(L2)C

l 2C 2

1H22N

4SnO

2Cl 2

5510

0(55162)

220

030

2112

(215

1)1221(1278)

998(1015)

4554(4572)

365

(402)

(p-C

lC6H

4CH

2)2Sn(L2)C

l 2C 2

1H20N

4SnO

2Cl 4

6197

9(62011)

200

032

1869(19

14)

2219

(2273)

889

(903)

4021(40

67)

302

(325)


Table2

1 Hand

13CNMRdata(120575

ppm)o

ftheop

hylline

complexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theoph

yllin

emoiety

ArndashH

ndashCH

2ndashH-8

ndashCH

3atN-3

ndashCH

3atN-1

ndashNHndash

Theoph

yllin

e(HL1)

mdashmdash

75-76(d1H

)36-37(s3H)

32(s3H)

104ndash106(br2

H)

(C6H

5CH

2)3Sn(L1)

79ndash81(m

15H

)36-37(s6H)

77-78(d1H

)39-40(s3H)

33(s3H)

mdash1787

(p-C

lC6H

4CH

2)3Sn(L1)

80ndash

82(m

12H

)39(s6H)

76-77(d1H

)41-4

2(s3H)

34(s3H)

mdash2401

(C6H

5CH

2)2Sn(L1)C

l79

-80(m

10H

)38(s4H)

75-76(d1H

)40-41(s3

H)

33-34(s3H)

mdash1721

(p-C

lC6H

4CH

2)2Sn(L1)C

l80-81(m8H)

37-38(s4H)

77-78(d1H

)40(s3H)

34-35(s3H)

mdash2350


Table3

1 Hand

13CNMRdata(120575

ppm)o

ftheob

rominec

omplexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theobrom

inem

oiety

ArndashH

ndashCH

2ndashndashC

H3atN-3

ndashCH

3atN-2

H-8

ndashNHndash

Theobrom

ine(L2)

mdashmdash

33(s3H)

35(s3H)

71(s1H)

130ndash132(br1H

)(C

6H5C

H2)

3Sn(L2)C

l70

ndash74(m

15H

)38-39(s6H)

34-35(s3H)

36-37(s3H)

77(s1H)

132ndash134(br1H

)1956

(p-C

lC6H

4CH

2)3Sn(L2)C

l71ndash73(m

12H

)39(s6H)

33-34(s3H)

36-37(s3H)

76(s1H)

134ndash136(br1H

)2534

(C6H

5CH

2)2Sn(L2)C

l 270

ndash73(m

10H

)39-40(s4H)

34(s3H)

37(s3H)

75(s1H)

133ndash135(br1H

)1834

(p-C

lC6H

4CH

2)2Sn(L2)C

l 271ndash73(m

8H)

38(s4H)

33-34(s3H)

36(s3H)

78(s1H)

133ndash136(br1H

)2366


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905



+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table1Ph

ysicalcharacteris

ticsa

ndanalyticaldataof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Empiric

alform

ula

MolW

tfoun

d(cal)


9times10minus2M)

Foun

d(cal)

SnCl

NC

H(C

6H5C

H2)

3Sn(L1)

C 28H

28N

4SnO

257076

(57124)

210

021

2019

(2077)

mdash96

1(98

0)5864(5887)

461

(494)

(p-C

lC6H

4CH

2)3Sn(L1)

C 28H

25N

4SnO

2Cl 3

67321

(67398)

170

019

1705

(176

1)1522(1569)

798(831

)4962(498

9)321

(373)

(C6H

5CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

51491

(51536)

240

024

2262(2303)

629

(684)

1038(1087)

4869(4894)

392

(410

)(p-C

lC6H

4CH

2)2Sn(L1)C

lC 2

1H21N

4SnO

2Cl

58261

(58385)

210

039

2006(2032)

1768

(1811)

926(959)

4299(4320)

302

(328)

(C6H

5CH

2)3Sn(L2)C

lC 2

8H29N

4SnO

2Cl

60681

(60750)

200

021

1916

(1953

)534

(580)

906(922)

5501(5535

)451

(481)

(p-C

lC6H

4CH

2)3Sn(L2)C

lC 2

8H26N

4SnO

2Cl 4

7092

9(71024)

150

029

1621(1671)

1931

(1985)

762(788)

4711

(4735)

329

(369)

(C6H

5CH

2)2Sn(L2)C

l 2C 2

1H22N

4SnO

2Cl 2

5510

0(55162)

220

030

2112

(215

1)1221(1278)

998(1015)

4554(4572)

365

(402)

(p-C

lC6H

4CH

2)2Sn(L2)C

l 2C 2

1H20N

4SnO

2Cl 4

6197

9(62011)

200

032

1869(19

14)

2219

(2273)

889

(903)

4021(40

67)

302

(325)


Table2

1 Hand

13CNMRdata(120575

ppm)o

ftheop

hylline

complexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theoph

yllin

emoiety

ArndashH

ndashCH

2ndashH-8

ndashCH

3atN-3

ndashCH

3atN-1

ndashNHndash

Theoph

yllin

e(HL1)

mdashmdash

75-76(d1H

)36-37(s3H)

32(s3H)

104ndash106(br2

H)

(C6H

5CH

2)3Sn(L1)

79ndash81(m

15H

)36-37(s6H)

77-78(d1H

)39-40(s3H)

33(s3H)

mdash1787

(p-C

lC6H

4CH

2)3Sn(L1)

80ndash

82(m

12H

)39(s6H)

76-77(d1H

)41-4

2(s3H)

34(s3H)

mdash2401

(C6H

5CH

2)2Sn(L1)C

l79

-80(m

10H

)38(s4H)

75-76(d1H

)40-41(s3

H)

33-34(s3H)

mdash1721

(p-C

lC6H

4CH

2)2Sn(L1)C

l80-81(m8H)

37-38(s4H)

77-78(d1H

)40(s3H)

34-35(s3H)

mdash2350


Table3

1 Hand

13CNMRdata(120575

ppm)o

ftheob

rominec

omplexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theobrom

inem

oiety

ArndashH

ndashCH

2ndashndashC

H3atN-3

ndashCH

3atN-2

H-8

ndashNHndash

Theobrom

ine(L2)

mdashmdash

33(s3H)

35(s3H)

71(s1H)

130ndash132(br1H

)(C

6H5C

H2)

3Sn(L2)C

l70

ndash74(m

15H

)38-39(s6H)

34-35(s3H)

36-37(s3H)

77(s1H)

132ndash134(br1H

)1956

(p-C

lC6H

4CH

2)3Sn(L2)C

l71ndash73(m

12H

)39(s6H)

33-34(s3H)

36-37(s3H)

76(s1H)

134ndash136(br1H

)2534

(C6H

5CH

2)2Sn(L2)C

l 270

ndash73(m

10H

)39-40(s4H)

34(s3H)

37(s3H)

75(s1H)

133ndash135(br1H

)1834

(p-C

lC6H

4CH

2)2Sn(L2)C

l 271ndash73(m

8H)

38(s4H)

33-34(s3H)

36(s3H)

78(s1H)

133ndash136(br1H

)2366


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905



+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table2

1 Hand

13CNMRdata(120575

ppm)o

ftheop

hylline

complexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theoph

yllin

emoiety

ArndashH

ndashCH

2ndashH-8

ndashCH

3atN-3

ndashCH

3atN-1

ndashNHndash

Theoph

yllin

e(HL1)

mdashmdash

75-76(d1H

)36-37(s3H)

32(s3H)

104ndash106(br2

H)

(C6H

5CH

2)3Sn(L1)

79ndash81(m

15H

)36-37(s6H)

77-78(d1H

)39-40(s3H)

33(s3H)

mdash1787

(p-C

lC6H

4CH

2)3Sn(L1)

80ndash

82(m

12H

)39(s6H)

76-77(d1H

)41-4

2(s3H)

34(s3H)

mdash2401

(C6H

5CH

2)2Sn(L1)C

l79

-80(m

10H

)38(s4H)

75-76(d1H

)40-41(s3

H)

33-34(s3H)

mdash1721

(p-C

lC6H

4CH

2)2Sn(L1)C

l80-81(m8H)

37-38(s4H)

77-78(d1H

)40(s3H)

34-35(s3H)

mdash2350


Table3

1 Hand

13CNMRdata(120575

ppm)o

ftheob

rominec

omplexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theobrom

inem

oiety

ArndashH

ndashCH

2ndashndashC

H3atN-3

ndashCH

3atN-2

H-8

ndashNHndash

Theobrom

ine(L2)

mdashmdash

33(s3H)

35(s3H)

71(s1H)

130ndash132(br1H

)(C

6H5C

H2)

3Sn(L2)C

l70

ndash74(m

15H

)38-39(s6H)

34-35(s3H)

36-37(s3H)

77(s1H)

132ndash134(br1H

)1956

(p-C

lC6H

4CH

2)3Sn(L2)C

l71ndash73(m

12H

)39(s6H)

33-34(s3H)

36-37(s3H)

76(s1H)

134ndash136(br1H

)2534

(C6H

5CH

2)2Sn(L2)C

l 270

ndash73(m

10H

)39-40(s4H)

34(s3H)

37(s3H)

75(s1H)

133ndash135(br1H

)1834

(p-C

lC6H

4CH

2)2Sn(L2)C

l 271ndash73(m

8H)

38(s4H)

33-34(s3H)

36(s3H)

78(s1H)

133ndash136(br1H

)2366


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905



+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table3

1 Hand

13CNMRdata(120575

ppm)o

ftheob

rominec

omplexes

Com

poun

d1 H

NMR

13CNMR

SnndashC

H2

ndashRmoiety

Theobrom

inem

oiety

ArndashH

ndashCH

2ndashndashC

H3atN-3

ndashCH

3atN-2

H-8

ndashNHndash

Theobrom

ine(L2)

mdashmdash

33(s3H)

35(s3H)

71(s1H)

130ndash132(br1H

)(C

6H5C

H2)

3Sn(L2)C

l70

ndash74(m

15H

)38-39(s6H)

34-35(s3H)

36-37(s3H)

77(s1H)

132ndash134(br1H

)1956

(p-C

lC6H

4CH

2)3Sn(L2)C

l71ndash73(m

12H

)39(s6H)

33-34(s3H)

36-37(s3H)

76(s1H)

134ndash136(br1H

)2534

(C6H

5CH

2)2Sn(L2)C

l 270

ndash73(m

10H

)39-40(s4H)

34(s3H)

37(s3H)

75(s1H)

133ndash135(br1H

)1834

(p-C

lC6H

4CH

2)2Sn(L2)C

l 271ndash73(m

8H)

38(s4H)

33-34(s3H)

36(s3H)

78(s1H)

133ndash136(br1H

)2366


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905



+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


+

+

+

N

N

O

O

N

N

N

N

O

O

N

N+

Sn

Sn

Sn

N

N

O

O

N

N

R

R

RR

R

R

R

R

R

CH3

CH3 CH3

CH3

CH3

CH3

∙

∙

∙∙

∙

∙+

C7H7N4O2

+

me 17906

C7H7N4O2

+

me 17906

C6H5N3O2

+

me 15104

C7H7N4O2

∙

me 17906

minusHCN

minusHNC

NH

N

N

O

O

N

NH C

HN

C

O

O

NH

NH

N

N

N

N

NH

CH

CH CH

CH

N

N

H

(b)

(a)

O

CH3

CH3

CH3

CH3

+

+

+

+

C

N

N

minusCO

minusCO

+ C

C4H5N3

me 9505

C5H5N3O∙+

me 12304

N

N

O

O

N

N

N

N

O

O

N

N

+

+

+

+N

N

O

O

N

N

R

R

R

Sn

Sn

Sn R

R

R

R

R

R

CH3

CH3

CH3

CH3

CH3

CH3∙

∙

∙+

C7H7N4O2

+

me 17905

C7H7N4O2

∙

me 17905



+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


+

+

N

N

O

O

N

N

H

N

N

O

O

N

N

H

Cl

N

N

O

O

N

N

H

R R

R

Sn

Sn

R R

Cl R

CH3

CH3

CH3

CH3CH3

CH3

∙+

∙+

∙+

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 18006

C7H8N4O2

∙+

me 180

C5H8N3

me 109

C5H7N3

me 109

C4H5N2

me 82

C4H5Nme 67

N

N

O

O

N

N

H

NO

N

N

H

minusHCNminusHCN

minusHNCON

N

O

N

N

NCH

NCH

CHCHN

N

N

N

H

(b)

(a)

Nme 55

NHC

NH

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH3CH3 ∙+

∙

∙

∙

∙+

∙+

N

N

N

minusCO

C6H7N3O∙+

me 137

O+

C+

+N

N

O

O

N

N

H

Sn

N

N

O

O

N

N

H

N

N

O

O

N

N

H

R R

RCl

Cl

Cl

R R

R

Sn

Sn

R R

R+

CH3

CH3

CH3

CH3

CH3

CH3∙+

∙+

∙+

C7H8N4O2

∙+

me 180

C7H8N4O2

me 180









(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of








(C6H5CH2)2Sn(L1)Cl




(C6H5CH2)3Sn(L2)Cl




(C6H5CH2)2Sn(L2)Cl2







119886






Sn

Cl

ClCl

Cl

N

N

N

N

OH

OCH3

CH2

CH2

H3C

Figure 2





Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table5Kinetic

parametersfor

thetherm

aldecompo

sitionof

theoph

yllin

eand

theobrom

inec

omplexes

Com

plex

Step

number

TempK

Coats-

Redfernmetho

dHorow

itz-M

etzger

metho

dDTA

119864119886kJm


1 molminus1 )

119864119886kJm


1 molminus1 )

Thermaleffect

Δ119867

(Jgminus

1 )

(C6H

5CH

2)3Sn(L1)

1483ndash673

5109

941

5423

1046

Exo

minus2042

2893ndash1003

30635

3762

31017

3801

Endo

9446

(p-C

lC6H

4CH

2)3Sn(L1)

144

3ndash633

4030

850

4184

881

Exo

minus1746

2873ndash973

21882

2742

24323

2982

Endo

9326

(C6H

5CH

2)2Sn(L1)C

l1

513ndash663

6382

1200

6562

1233

Exo

minus2210

2703ndash773

1915

43206

2114

03326

Exo

minus8999

3893ndash973

36698

4541

35353

443

Endo

9042

(p-C

lC6H

4CH

2)2Sn(L1)C

l1

483ndash673

5470

1054

5523

1067

Exo

minus2169

2723ndash793

25529

3942

23849

3764

Exo

minus9246

3873ndash973

38294

4745

38048

4785

Endo

9291

(C6H

5CH

2)3Sn(L2)C

l1

473ndash653

3829

697

4046

795

Exo

minus3046

2723ndash813

8703

1206

9534

1383

Exo

minus5249

3893ndash1003

20812

2410

21731

2622

Endo

11112

(p-C

lC6H

4CH

2)3Sn(L2)C

l1

423ndash623

3191

620

3491

741

Exo

minus2962

2703ndash753

25529

4162

25021

4069

Exo

minus5162

3873ndash973

2393

33041

25095

3189

Endo

11342

(C6H

5CH

2)2Sn(L2)C

l 21

493ndash653

5744

1120

5855

1135

Exo

minus2994

2703ndash773

2815

74369

27433

4344

Exo

minus5160

3873ndash993

17632

2142

17857

2157

Endo

11021

(p-C

lC6H

4CH

2)2Sn(L2)C

l 21

473ndash653

5444

784

5645

826

Exo

minus3106

2723ndash793

1914

72947

19218

2971

Exo

minus5206

3873ndash973

23753

2901

24328

2999

Endo

11226





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





HL1 8 10 12 16 9 12 11 14(C6H5CH2)3Sn(L

1) 10 12 13 17 10 13 10 12(p-ClC6H4CH2)3Sn(L

1) 9 10 13 15 12 14 12 13(C6H5CH2)2Sn(L

1)Cl 9 12 10 13 9 11 10 11(p-ClC6H4CH2)2Sn(L

1)Cl 11 14 15 18 12 14 14 16L2 9 11 13 17 11 15 12 14(C6H5CH2)3Sn(L

2)Cl 9 11 15 19 12 16 14 16(p-ClC6H4CH2)3Sn(L

2)Cl 10 13 14 17 11 13 13 15(C6H5CH2)2Sn(L

2)Cl2 11 15 16 19 13 17 14 16(p-ClC6H4CH2)2Sn(L

2)Cl2 10 11 12 16 10 14 11 13




HL1 33 42 39 48(C6H5CH2)3Sn(L

1) 60 79 63 77(p-ClC6H4CH2)3Sn(L

1) 55 61 65 79(C6H5CH2)2Sn(L

1)Cl 48 61 62 69(p-ClC6H4CH2)2Sn(L


2)Cl 42 56 50 67(p-ClC6H4CH2)3Sn(L

2)Cl 52 64 58 73(C6H5CH2)2Sn(L

2)Cl2 58 68 64 76(p-ClC6H4CH2)2Sn(L

2)Cl2 62 73 68 82Bavistin 82 96 84 98

References





















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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