REACTIVITY STUDIES OF CYCLOPENTADIENYL
COMPLEXES OF GROUP 6 METALS WITH
ARYLSULFIDES, ORGANO P-S AND P-Se
HETEROCYCLES AND ARYLTHIOLATE
PHOSPHINE LIGANDS
OOI MEI LEE
THESIS SUBMITTED IN FULFILMENT OF
THE REQUIREMENT FOR THE DEGREE
OF DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMISTRY
FACULTY OF SCIENCE
UNIVERSITY OF MALAYA
KUALA LUMPUR
2011
i
ABSTRACT
The reactivity of [CpM(CO)3]2 (M = Cr (1), Mo (3)) together with their
congeners, [CpM(CO)2]2 (M = Cr (2), Mo (4)) towards alkyl sulfides such as bibenzyl
di- and trisulfide, organophosphorus chalcogen heterocycles such as 2,4-bis(p-
tolylthio)1,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy’s reagent), 1,3,2,4-
dithiadiphosphetane 2,4-diselenides (Woollins’ Reagent) and thioarylphosphines have
been investigated. Reactions that occurred under mild conditions for 1 was found to
proceed via the highly reactive monomer radical, CpCr(CO)3·. However, the reactions
with 2 and 4 required more forcing conditions at elevated temperature.
Forty metal complexes were synthesized and characterized in this work. All the
products were elucidated via IR, 1H,
13C and
31P NMR, LCMS, elemental analyses and
single crystal x-ray diffraction. Mechanistic pathways were proposed for most of the
reactions investigated based on evidence obtained from thermolysis, NMR and mass
spectra studies. The outcomes of this work are summarized below.
(i) The reaction of 1 with Bz2S2 at R.T. gave [CpCr(CO)2(SBz)]2 (6) followed by
[CpCr(CO)2]2S (5) and [CpCr(SBz)]2S (7) as secondary products which undergo
complete decarbonylation to give the final thermolyzed product Cp4Cr4S4 (8). It
is postulated that the formation of 6 proceeds via the 17e- radical pathway which
involves S-S bond cleavage of the ligand.
At elevated temperature, reaction of 4 with Bz2S2 gave isomeric trans-syn and
trans-anti [CpMo(CO)(SBz)]2 (12a, b), [CpMo(SBz)S]2 (10) and
[CpMo(CO)(SBz)]2S (11) as main products.
(ii) The facile reaction of [CpCr(CO)3]2 (1) with Bz2S3 at ambient temperature has
led to the isolation of [CpCr(CO)2(SBz)]2 (6) with [CpCr(SBz)]2S (7) as main
products. Thermolytic studies showed that 6 underwent complete
ii
decarbonylation to give [CpCr(SBz)]2S (7). Prolonged thermolysis of 6 and 7
led to decomposition which eventually yielded Cp4Cr4S4 (8).
The reaction of [CpMo(CO)3]2 (3) with Bz2S3 at an elevated temperature
afforded [CpMo(CO)2(SBz)]2 (9), [CpMo(CO)(SBz)]2S (11),
[CpMo(CO)(SBz)]2 (12) and [CpMo(SBz)S]2 (10). Thermolytic studies showed
that 9 underwent stepwise decarbonylation to give 11 and 10. The totally
decarbonylated 10 was isolated as two polymorphs.
(iii) The reaction of 4 with an equivalent of 2,4-bis(p-tolylthio) 1,3-dithia-2,4-
diphosphetane-2,4-disulfide (Davy’s reagent) led to the isolation of
CpMo(CO)2(S2P(SC6H4Me)2) (14), Cp2Mo2(CO)5(S2P(SC6H4Me)) (15) and
Cp2Mo2(µ-S)(µ-S2)(µ-SC6H4Me) (16) with yields dependent on reaction
conditions. However, reaction of 4 with half an equivalent of Davy’s reagent
gave Cp2Mo2(CO)5(S2P(SC6H4Me)) (15), trans-syn/trans-anti-isomer of
[CpMo(CO)(SC6H4Me)]2 (17), Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me)2 (18),
[CpMo(CO)2S]2 (19) and Cp3Mo3(µ-S)2(µ-S2)(µ3-S) (20). Thermolytic studies
followed by 1H NMR spectroscopy analyses indicated that 14 and 15 had
degraded to 16. The postulated mechanism involves P–S bond cleavage in
Davy’s reagent leading to a ring opening and desulfurization process.
(iv) The reaction of 1 with 1,3,2,4-dithiadiphosphetane 2,4-diselenides or Woollins’
Reagent at ambient temperature gave mainly [CpCr(CO)2]2Se (21) but with an
excess of 1, trans-[CpCr(CO)2(SePPh)]2 (22) was isolated. However thermolytic
reaction with the triply bonded congener Cp2Cr2(CO)4 (2) led to the isolation of
trans-[CpCr(CO)2(SePPh)]2 (22), CpCr(CO)2(SeP(H)Ph) (23) and
[CpCr(Se2P(O)Ph)]2 (24). The ring-opening reaction of Woollins’ Reagent via
iii
an initial homolytic P-Se bond cleavage by CpCr(CO)n· (n = 2 (2A) or 3 (1A))
depicts a new approach to coordination chemistry involving P-Se based ligands.
The thermolytic reaction of 4 with Woollins’ reagent led to the isolation of
[Cp2Mo2{(µ-Se)2(PPh(Se))}{(µ-Se)(PPh)3}] (25), Cp4Mo4(CO)3Se4 (26) and a
pair of polymorphic products of Cp3Mo3(CO)4[Se3(PPh)2] (27a, b). A dual
pathway via the 15 e- radical, CpMo(CO)2· and the triply-bonded complex 4,
was indicated.
(v) Reactivity studies of 1 and 3 towards P(C6H4SMe-p)3, PPh2(C6H4SMe-o),
PPh(C6H4SMe-o)2 and P(C6H4SMe-o)3 under varying reaction conditions have
led to the isolation of sixteen products. The (P, S) donor ligands of P(C6H4SMe-
p)3, PPh2(C6H4SMe-o), PPh(C6H4SMe-o)2 and P(C6H4SMe-o)3 having one, two
and three thiomethylphenyl groups, preferred mono-, bi- and tridentate
coordination modes, respectively.
(vi) The facile adduct formation of [CpCr(SBz)]2S (7) and [CpMo(SBz)(S)]2 (10)
with 2 moles equivalents of Fe2(CO)9 was found to give both mono- and
dimetallated complexes [Cp2Cr2(SBz)]S2[Fe(CO)3] (44), [CpMo]2S4[Fe(CO)3]2
(45), [CpMo]2S3[Fe(CO)3]2 (46) and [CpMo(SBz)]2S2[Fe(CO)2] (47),
respectively.
(vii) The thermolytic reaction of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) with a mole
equivalent of 1 gave [CpMo(CO)2(µ-S)]2 (19), [CpMo(CO)(SC6H4Me)]2 (17)
[CpCr(µ-SC6H4Me)]2S (48) and Cp4Cr4S4 as products.
iv
ABSTRAK
Kereaktifan [CpM(CO)3]2 (M = Cr (1), Mo (3)) bersama-sama dengan kongener
mereka, [CpM(CO)2]2 (M = Cr (2), Mo (4)) terhadap alkil sulfida seperti bibenzyl di- dan
trisulfida, heterosikal kalkogen organofosfat seperti 2,4-bis (p-tolylthio) 1,3-dithia-2,4-
diphosphetane-2,4-disulfida (reagen Davy), 1,3,2,4-dithiadiphosphetana 2,4-diselenida
(reagen Woollins’) dan thioarylfosfine telah diselidik. Tindak balas yang terjadi pada suhu
bilik untuk 1 didapati bermula melalui monomer radikal yang sangat reaktif, CpCr(CO)3·.
Namun, tindak balas dengan 2 dan 4, telah dilakukan pada suhu yang lebih tinggi dari
biasa.
Empat puluh kompleks logam telah disintesis dan dicirikan dalam penyelidikan ini.
Semua produk tersebut telah dikenalpastikan melalui IR, 1H,
13C dan
31P NMR, LCMS,
analisis elemental dan kristal tunggal x-ray difraksi. Mekanisma tindak balas telah
dicadangkan untuk sebahagian besar tindak balas yang diselidiki dengan bantuan bukti
yang diperolehi dari termolisis, NMR dan kajian spektra jisim. Keputusan penyelidikan ini
adalah seperti berikut.
(i) Tindak balas 1 dengan Bz2S2 pada suhu bilik menghasilkan [CpCr(CO)2(SBz)]2 (6)
diikuti oleh [CpCr(CO)2]2S (5) dan [CpCr(SBz)]2S (7) sebagai hasil sekunder yang
mengalami kehilangan karbon dioksida yang lengkap untuk memberi Cp4Cr4S4 (8)
sebagai hasil terakhir daripada proses pemanasan. Dari keputusan ini dicadangkan
bahawa pembentukan 6 dimulakan dengan 17e-radikal yang melibatkan pemutusan
ikatan S-S dalam ligan.
Pada suhu yang tinggi, 4 bertindak dengan Bz2S2 dan memberikan hasil isomerik
trans-syn serta trans-anti [CpMo(CO)(SBz)]2 (12a, b), [CpMo(SBz)S]2 (10) dan
[CpMo(CO)(SBz)]2S (11) sebagai hasil utama.
v
(ii) Tindak balas yang mudah iaitu antara [CpCr(CO)3]2 (1) dengan Bz2S3 pada suhu
bilik telah menghasilkan [CpCr(CO)2(SBz)]2 (6) dan [CpCr(SBz)]2S (7) sebagai
hasil utama, kedua-duanya telah diasingkan. Kajian pemanasan menunjukkan
bahawa 6 mengalami kehilangan karbon dioksida yang lengkap untuk memberikan
[CpCr(SBz)]2S (7). Proses pemanasan yang panjang untuk 6 dan 7 menyebabkan
penguraian yang akhirnya menghasilkan Cp4Cr4S4 (8).
Suhu yang lebih tinggi diperlukan untuk tindak balas [CpMo(CO)3]2 (3) dengan
Bz2S3 untuk menghasilkan [CpMo(CO)2(SBz)]2 (9), [CpMo(CO)(SBz)]2S (11),
[CpMo(CO)(SBz)]2 (12) and [CpMo(SBz)S]2 (10). Kajian termolitik menunjukkan
bahawa 9 mengalami kehilangan karbon dioksida secara berperingkat untuk
memberikan 11 dan 10. Kompleks 10 yang telah mengalami kehilangan semua
karbon dioksida telah diasingkan sebagai dua polimorf.
(iii) Reaksi 4 dengan 2,4-bis(p-tolylthio) 1,3-dithia-2,4-diphosphetane-2,4-disulfida
(reagen Davy) yang sama kemolaran telah menghasilkan CpMo(CO)2(S2P(SC6H4
Me)2) (14), Cp2Mo2(CO)5(S2P(SC6H4Me)) (15) and Cp2Mo2(µ-S)(µ-S2)(µ-SC-
6H4Me) (16) dengan peratusan hasil bergantung pada keadaan reaksi. Namun,
reaksi 4 dengan 0.5 molar reagen Davy memberikan Cp2Mo2(CO)5(S2P(SC-
6H4Me)) (15), trans-syn/trans-anti-isomer [CpMo(CO)(SC6H4Me)]2 (17),
Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me)2 (18), [CpMo(CO)2S]2 (19) dan Cp3Mo3(µ-
S)2(µ-S2)(µ3-S) (20). Kajian termolitik yang diikuti dengan 1H NMR menunjukkan
bahawa 14 dan 15 telah bertukar ke 16. Mekanisme yang dicadangkan melibatkan
belahan ikatan P-S dalam reagen Davy diikuti dengan pembukaan gelang dan
proses nyah sulfur.
vi
(iv) Tindak balas 1 dengan 1,3,2,4-dithiadiphosphetana2,4-diselenida atau reagen
Woollins' pada suhu bilik telah memberikan [CpCr(CO)2]2Se (21) sebagai hasil
utama, tetapi dengan 1 yang berlebihan, trans-[CpCr(CO)2(SePPh)]2 (22) telah
dihasilkan. Namun, tindak balas pemanasan dengan kongener ikatan ganda tiga,
Cp2Cr2(CO)4 (2) menyebabkan pengasingan trans-[CpCr(CO)2(SePPh)]2 (22),
CpCr(CO)2(SeP(H)Ph) (23) and [CpCr(Se2P(O)Ph)]2 (24). Tindak balas yang
melibatkan pembukaan gelang pada reagen Woollins' dimula oleh CpCr(CO)n· (n =
2 (2A) or 3 (1A)) melalui pembelahan ikatan P-Se secara homolitik
menggambarkan pendekatan baru untuk kimia koordinatan yang melibatkan ligan
jenis P-Se.
Tindak balas termolitik dari 4 dengan reagen Woollins' menyebabkan pengasingan
[Cp2Mo2{(µ-Se)2(PPh(Se))}{(µ-Se)(PPh)3}] (25), Cp4Mo4(CO)3Se4 (26) dan
sepasang produk polimorfik dari Cp3Mo3(CO)4[Se3(PPh)2] (27a, b). Dua lalui
melalui 15 e-radikal, CpMo(CO)2· dan ikatan ganda tiga kompleks 4 telah
dikenalpasti.
(v) Kajian kereaktifan 1 dan 3 terhadap P(C6H4SMe-p)3, PPh2(C6H4SMe-o), PPh(C-
6H4SMe-o)2 dan P(C6H4SMe-o)3 dalam pelbagai keadaan tindak balas telah
menyebabkan pengasingan enam belas produk. Ligan penderma (P, S) seperti
P(C6H4SMe-p)3, PPh2(C6H4SMe-o), PPh(C6H4SMe-o)2 dan P(C6H4SMe-o)3
masing-masing mempunyai satu, dua dan tiga kumpulan tiomethylphenyl, lebih
cenderung kepada cara koordinasi dalam mono-, bi- dan tridentate.
(vi) Pembentukan aduk yang mudah dari [CpCr(SBz)]2S (7) dan [CpMo(SBz)(S)]2 (10)
dengan 2 molar Fe2(CO)9 yang setara telah dikenalpasti masing-masing untuk
memberi mono dan kompleks dwilogam [Cp2Cr2(SBz)]S2[Fe(CO)3] (44),
vii
[CpMo]2S4[Fe(CO)3]2 (45), [CpMo]2S3[Fe(CO)3]2 (46) dan
[CpMo(SBz)]2S2[Fe(CO)2] (47).
(vii) Reaksi termolytik dari [CpMo(CO)2(S2P(SC6H4Me)2)] (14) dengan molar setara 1
memberikan [CpMo(CO)2(µ-S)]2 (19), [CpMo(CO)(SC6H4Me)]2 (17) [CpCr(µ-
SC6H4Me)]2S (48) and Cp4Cr4S4 sebagai hasil.
viii
ACKNOWLEDGEMENTS
I wish to express my deepest gratitude and appreciation to Assoc. Prof. Dr.
Richard Wong Chee Seng for his inspiring guidance, supervision, invaluable advice and
keen interest throughout the course of this study. I would also like to thank my co-
supervisor, Prof. Dr. Tan Guan Huat for his advice and guidance especially during the
LCMS analysis and his kindness and patience during the final hectic months needed to
complete the thesis. Assistance from Prof. Dr. Ng Seik Weng and Prof. Dr. Ward T.
Robinson for the X-ray diffraction analyses of most of the complexes, Assoc. Prof. Dr.
Noel F. Thomas (advice in proposing certain mechanism), Miss Norzalida Zakaria (NMR
spectroscopy analysis) and Mr. Siew Yau Foo (LCMS analysis), respectively, are also
gratefully acknowledged.
I would like to sincerely thank my colleague Miss Chan Chun Foong and my
juniors Miss Elizabeth Fong Yew Mei, Miss Ngue Chin May, Mr. Ngan Ngui Khiong
and Mr. Ang Chun Hui for their advice and support during my study.
I would also like to thank University Of Malaya for granting a tutorship and
scholarship (Biasiswazah Tuanku Pro-Cancelor) throughout my study. Research grants
from the Academy of Sciences, Malaysia (SAGA), MOSTI (Science Fund) and UMRG
(Cluster Fund) are gratefully acknowledged.
Finally, I like to dedicate this work to my ever supportive parents and my siblings.
ix
TABLE OF CONTENTS
Page
ABSTRACT . . . i
ABSTRAK . . . iv
ACKNOWLEDGEMENTS . . . viii
TABLE OF CONTENTS . . . ix
LIST OF FIGURES . . . xxiv
LIST OF TABLES . . . xxvii
LIST OF ABBREVIATIONS . . . xxxiii
CHAPTER I INTRODUCTION
1.1 A brief review on the reactivity of [CpM(CO)n]2 [M = Cr, n = 3 (1)
or n = 2 (2); M = Mo, n = 3 (3) or n = 2 (4)]
1.1.1 Biscyclopentadienyldichromiumhexacarbonyl,
[CpCr(CO)3]2 (1) . . . 1
1.1.2 Biscyclopentadienyldichromiumtetracarbonyl,
[CpCr(CO)2]2 (2) . . . 2
1.1.3 Biscyclopentadienyldimolybdenumhexacarbonyl,
[CpMo(CO)3]2 (3) . . . 2
1.1.4 Biscyclopentadienyldimolybdenumtetracarbonyl,
[CpMo(CO)2]2 (4) . . . 3
1.2 A review on the synthesis and reactivity of molybdenum and
chromium with organochalcogenide ligand . . . 4
1.2.1 Organochalcogenide derivatives of molybdenum complexes . . . 4
1.2.2 Organochalcogenide derivatives of chromium complexes . . . 18
1.3 A review on the synthesis and reactivity of molybdenum and
chromium with mixed pnicogen/chalcogen ligands . . . 21
x
1.3.1 Mixed pnicogen-chalcogen derivatives of molybdenum
complexes . . . 22
1.3.2 Mixed pnicogen-chalcogen derivatives of chromium
complexes . . . 24
1.4 A review on the synthesis and reactivity of molybdenum and
chromium with tertiary phosphine ligands . . . 31
1.4.1 Synthesis and reactivity of molybdenum tertiary phosphine
complexes . . . 32
1.4.2 Synthesis and reactivity of chromium tertiary phosphine
complexes . . . 33
1.5 Objectives . . . 35
CHAPTER II RESULTS AND DISCUSSION
2.1 Studies with bibenzyl trisulfide
2.1.1 The reaction of [CpCr(CO)3]2 (1) with Bibenzyl Trisulfide . . . 36
2.1.2 The reaction of [CpCr(CO)2]2 (2) with Bibenzyl Trisulfide . . . 37
2.1.3 Thermolysis Studies
(a) Thermolysis of [CpCr(CO)2(SBz)]2 (6) . . . 37
(b) Thermolysis of [CpCr(SBz)]2S (7) . . . 37
2.1.4 NMR spectral studies
(a) Reaction of [CpCr(CO)2 ]2S (5) with Bz2S3 at 60 °C . . . 38
(b) Reaction of [CpCr(CO)2(SBz)]2 (6) with Bz2S3 at
ambient temperature . . . 38
2.1.5 Mechanistic pathways: Formation of [CpCr(CO)2(SBz)]2 (6) and
[CpCr(SBz)]2S (7) . . . 39
2.1.6 Physical properties . . . 41
2.1.7 Spectral characteristics
2.1.6.1 IR spectra . . . 41
2.1.6.2 NMR spectra . . . 42
2.1.6.3 Mass spectra . . . 42
xi
2.1.8 Molecular structure . . . 44
2.2 Studies of [CpMo(CO)3]2 (3) with Bibenzyl Trisulfide
2.2.1 The reaction of [CpMo(CO)3]2 (3) with equimolar of Bibenzyl
Trisulfide . . . 46
2.2.2 NMR spectral studies
(a) Reaction of [CpMo(CO)2(SBz)]2 with Bz2S3 at 60 °C . . . 46
(b) Reaction of [CpMo(CO)(SBz)]2S (11) with Bz2S3
at 110 °C . . . 47
2.2.3 Thermolysis studies of [CpMo(CO)2(SBz)]2 (9) and
[CpMo(CO)(SBz)]2S (11) . . . 47
2.2.4 Mechanistic pathways : Formation of [CpMo(CO)2(SBz)]2 (9),
[CpMo(SBz)S]2 (10a & b) and [CpMo(CO)(SBz)]2S (11) . . . 48
2.2.5 Physical properties . . . 50
2.2.6 Spectral properties
2.2.6.1 IR spectra . . . 50
2.2.6.2 NMR spectra . . . 51
2.2.7 Molecular Structures . . . 52
2.3 Studies of [CpCr(CO)3]2 (1) with Bibenzyl Disulfide
2.3.1 Study of [CpCr(CO)3]2 (1) with equimolar of Bibenzyl
Disulfide . . . 59
2.3.2 Study of [CpCr(CO)2]2 (2) with equimolar of Bibenzyl
Disulfide . . . 59
2.3.3 NMR spectral studies
(a) Reaction of [CpCr(CO)2]2 (2) with equimolar of
Bibenzyl Disulfide at 60 ºC . . . 60
(b) Reaction of [CpCr(CO)2]2S (5) equimolar of
Bibenzyl Disulfide at 60 ºC . . . 61
2.3.4 Mechanistic pathways : Formation of [CpCr(CO)2(SBz)]2 (6)
and [CpCr(SBz)]2S (7) . . . 61
2.3.5 Molecular structure . . . 64
2.4 Studies of [CpMo(CO)2]2 (4) with Bibenzyl Disulfide
2.4.1 The reaction of [CpMo(CO)2]2 (4) with equimolar of Bibenzyl
xii
Disulfide . . . 67
2.4.2 NMR spectral studies
(a) Thermolysis of trans-anti[CpMo(CO)(SBz)]2 (12b)
at 110 °C . . . 67
(b) Cothermolysis of trans-syn [CpMo(CO)(SBz)]2 (12a)
with equimolar of Bz2S2 at 110 °C . . . 70
(c) Reaction of [CpMo(CO)3]2 (3) with equimolar of Bz2S2
at 60 °C . . . 70
2.4.3 Cothermolysis study
(a) Reaction of trans-syn [CpMo(CO)(SBz)]2 (12a) with
equimolar of bibenzyl disulfide at 110 °C . . . 70
2.4.4 Solventless reaction at 110 °C for 2h . . . 71
2.4.5 Mechanistic pathways: Formation of doubly bonded isomers of
trans-syn/trans-anti [CpMo(CO)(SBz)]2 (12a&b ) and
[CpMo(SBz)]4 (13) . . . 73
2.4.6 Physical Properties . . . 75
2.4.7 Spectral properties
2.4.7.1 I.R spectra . . . 75
2.4.7.2 NMR spectra . . . 76
2.4.7.3 Mass spectra . . . 77
2.4.8 Molecular Structures . . . 78
2.5 Studies of [CpMo(CO)2]2 (4) with Davy’s Reagent (DR)
2.5.1 The reaction of [CpMo(CO)2]2 (4) with equimolar of Davy’s
Reagent (DR) . . . 82
2.5.2 The reaction of [CpMo(CO)2]2 (4) with 0.5 equimolar of Davy’s
Reagent (DR) . . . 83
2.5.3 NMR thermolytic studies
(a) Thermolysis of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) . . . 84
(b) Thermolysis of Cp2Mo2(CO)5(S2P(SC6H4Me)) (15) . . . 84
xiii
(c) Cothermolysis of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) with
Davy’s reagent (DR) at 110 °C . . . 84
(d) Cothermolysis of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) with
[CpMo(CO)2]2 at 110 °C . . . 84
(e) Thermolysis of [CpMo(CO)(SC6H4Me)]2 (17) at 110 °C . . . 85
(f) Thermolysis of Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me)2 (18)
at 110 °C . . . 85
(g) Cothermolysis of [CpMo(CO)2(µ-S)]2 (19) with
Davy’s reagent (DR) . . . 85
(h) Thermolysis of [Cp2Mo2(µ-S)(µ-S2)(µ-SC6H4Me)] (16) . . . 85
2.5.4 Mechanistic pathways
2.5.4.1 Mechanistic pathways of the reaction of [CpMo(CO)2]2 (4)
with an equimolar amount of Davy’s Reagent (DR) . . . 86
2.5.4.2 Mechanistic pathways of the reaction of [CpMo(CO)2]2 (4)
with 0.5 mole equivalent of Davy’s Reagent (DR) . . . 89
2.5.5 Physical properties . . . 91
2.5.6 Spectral properties
2.5.6.1 IR spectra . . . 93
2.5.6.2 NMR spectra . . . 94
2.5.6.3 Mass spectra . . . 96
2.5.7 Molecular structures . . . 100
2.6 Studies of [CpCr(CO)3]2 (1) with Woollins’ Reagent
2.6.1 The reaction of [CpCr(CO)3]2 (1) with an equimolar amount of
Woollins’ Reagent . . . 108
2.6.2 The reaction of [CpCr(CO)2]2 (4) with equimolar of Woollins’
Reagent . . . 109
2.6.3 NMR spectral studies
(a) Thermolysis of CpCr(CO)2(SeP(H)Ph) (23) . . . 110
(b) Thermolysis of trans-[CpCr(CO)2(SePPh)]2 (22) . . . 110
(c) Thermolysis of Cp2Cr2(Se2P(O)Ph)2 (24) . . . 111
xiv
(d) Cothermolysis of CpCr(CO)2(SeP(H)Ph) (23) and Woollins’
Reagent . . . 111
2.6.3 Mechanistic Pathway: Formation of the Cp2Cr2(CO)4Se (21), trans-
[CpCr(CO)2(SePPh)]2 (22), CpCr(CO)2(SeP(H)Ph) (23) and
[CpCr(Se2P(O)Ph)]2 (24). . . . 112
2.6.4 Physical properties . . . 114
2.6.5 Spectral properties
2.6.5.1 IR spectra . . . 115
2.6.5.2 NMR spectra . . . 116
2.6.5.3 Mass spectra . . . 117
2.6.6 Molecular structures . . . 119
2.7 Studies of [CpMo(CO)2]2 (2) with Woollins’ Reagent
2.7.1 The reaction of [CpMo(CO)2]2 (2) with equimolar of
Woollins’ Reagent . . . 128
2.7.2 Mechanistic pathways : Formation of [Cp2Mo2{(µ-Se)2(PPh(Se))
{(µ-Se)(PPh)3}] (25), Cp4Mo4(CO)3Se4 (26) and
Cp3Mo3(CO)4[Se3(PPh)2] (27a & b) . . . 128
2.7.3 Physical properties . . . 131
2.7.4 Spectral characteristics
2.7.4.1 IR spectra . . . 132
2.7.4.2 NMR spectra . . . 133
2.7.4.3 Mass spectra . . . 139
2.7.5 Molecular structures . . . 141
2.8 Studies with P(C6H4SMe-p)3
2.8.1 Reaction of Cp2Cr2(CO)6 (1) and Cp2Cr2(CO)4 (2) with
P(C6H4SMe-p)3 . . . 144
2.8.2 Proposed Structure for 28 . . . 144
2.8.3 Physical properties . . . 149
2.8.4 Spectral characteristics
2.8.4.1 IR spectrum . . . 146
2.8.4.2 NMR spectrum . . . 146
2.8.4.3 Mass spectrum . . . 147
xv
2.9 Studies of Cp2Mo2(CO)6 (3) and Cp2Mo2(CO)4 (2) with P(C6H4SMe-p)3
2.9.1 Reaction of Cp2Mo2(CO)6 (3) and Cp2Mo2(CO)4 with
P(C6H4SMe-p)3 . . . 148
2.9.2 Mechanistic pathways : Formation of Cp2Mo2(CO)5{P(C6H4SMe-p)3}(29),
Cp2Mo2(CO)(µ-CO)2{P(C6H4SMe-p)3} (30) and
Cp4Mo4(CO)4(µ3-O)(µ2-O)2(O) (31) . . . 148
2.9.3 Physical properties . . . 150
2.9.4 Spectral properties
2.9.4.1 IR spectra . . . 151
2.9.4.2 NMR spectra . . . 151
2.9.4.3 Mass spectra . . . 153
2.9.5 Molecular structures . . . 154
2.10 Studies of [CpCr(CO)3]2 (1) with PPh2(C6H4SMe-o)
2.10.1 The reaction of [CpCr(CO)3]2 (1) with 2.5 mole equivalent of
PPh2(C6H4SMe-o) . . . 160
2.10.2 NMR tube reaction of [CpCr(CO)2]2 (2) with 2.5 mole
equivalent of PPh2(C6H4SMe-o) . . .160
2.10.3 Mechanistic pathways:
Formation of CpCr(CO)2{o-(C6H4S)PPh2}(32) . . .160
2.10.4 Physical Properties . . . 162
2.10.5 Spectra Characteristics
2.10.5.1IR spectrum . . . 162
2.10.5.2NMR spectrum . . . 162
2.10.5.3Mass spectrum . . . 163
2.10.6 Molecular structure . . . 164
2.11 Studies of [CpCr(CO)3]2 (1) with PPh(C6H4SMe-o)2
2.11.1 The reaction of [CpCr(CO)3]2 (1) with PPh(C6H4SMe-o)2 . . . 165
2.11.2 The reaction of [CpCr(CO)2]2 (2) with PPh(C6H4SMe-o)2 . . . 165
2.11.3 NMR Tube Reaction
(a) The reaction of [CpCr(CO)3]2 (1) with PPh(C6H4SMe-o)2 . . . 166
2.11.4 Mechanistic pathways: Formation of [Cp2Cr2(CO)
{(µ-SC6H4)2PPh}] (33) and CpCr{(µ-SC6H4)2PPh} (34) . . . 166
xvi
2.11.5 Physical Properties . . . 169
2.11.6 Spectra Characteristics
2.11.6.1 IR spectra . . . 169
2.11.6.2 NMR spectra . . . 170
2.11.6.3 Mass spectra . . . 170
2.11.7 Molecular structures . . . 171
2.12 Studies of [CpCr(CO)3]2 (1) with P(C6H4SMe-o)3
2.12.1 The reaction of [CpCr(CO)3]2 (1) with P(C6H4SMe-o)3 . . . 174
2.12.2 The reaction of [CpCr(CO)2]2 (2) with P(C6H4SMe-o)3 . . . 174
2.12.3 NMR Tube Reaction
The reaction of [CpCr(CO)3]2 (1) with P(C6H4SMe-o)3 at 80 °C in
C6D6 . . . 174
2.12.4 Mechanistic pathway: Formation of
[Cp2Cr2(CO){(µ-SC6H4)2(C6H4SMe-o)P}] (35) . . . 176
2.12.5 Physical properties . . . 177
2.12.6 Spectral characteristics
2.12.6.1 IR spectrum . . . 177
2.12.6.2 NMR spectrum . . . 177
2.12.6.3 Mass spectrum . . . 178
2.12.7 Molecular structure . . . 178
2.13 Studies of [CpMo(CO)2]2 (4) with PPh2(C6H4SMe-o)
2.13.1 The reaction of [CpMo(CO)2]2 (4) with PPh2(C6H4SMe-o) . . . 180
2.13.2 Mechanistic pathways: Formation of CpMo(CO)2{(C6H4S-o)PPh2}(36)
. . . 180
2.13.3 Physical Properties . . . 181
2.13.4 Spectra Characteristics
xvii
2.13.4.1 IR spectrum . . . 181
2.13.4.2 NMR spectrum . . . 181
2.13.4.3 Mass spectrum . . . 182
2.13.5 Molecular structure . . . 182
2.14 Studies of [CpMo(CO)2]2 (4) with PPh(C6H4SMe-o)2
2.14.1 The reaction of [CpMo(CO)2]2 (4) with an equimolar of amount of
PPh(C6H4SMe-o)2 . . . 184
2.14.2 Mechanistic pathways: Formation of CpMo(CO)3H (37),
[Cp2Mo2(CO){(µ-SC6H4)2PPh}] (38) and
CpMo(CO){(µ-SC6H4)(µ-C6H4SMe-o)PPh} (39) . . . 184
2.14.3 Physical properties . . . 187
2.14.4 Spectral characteristics
2.14.4.1 IR spectrum . . . 187
2.14.4.2 NMR spectra . . . 188
2.14.4.3 Mass spectra . . . 189
2.14.5 Molecular structures . . . 190
2.15 Studies of [CpMo(CO)2]2 (4) with P(C6H4SMe-o)3
2.15.1 The reaction of [CpMo(CO)2]2 (4) with one equivalent of
P(C6H4SMe-o)3 . . . 193
2.15.2 NMR Tube Reactions
(a) Thermolysis of [Cp2Mo2(CO){(µ-SC6H4)2(C6H4SMe-o)P}] (41)
. . . 193
(b) Thermolysis of Mo(CO)3{P(C6H4SMe-o)3} (42) . . . 193
2.15.3 Mechanistic pathways : Formation of [Cp2Mo2(CO){(µ-SC6H4)2(o-
C6H4SCH2)P}] (40), [Cp2Mo2(CO){(µ-SC6H4)2(C6H4SMe-o)P}] (41),
Mo(CO)3{P(C6H4SMe-o)3} (42) and CpMo2(CO)3(µ-S){(µ-SC6H4)
xviii
(C6H4SMe-o)P} (43) . . . 194
2.15.4 Physical properties . . . 196
2.15.5 Spectral properties
2.15.5.1 IR spectra . . . 197
2.15.5.2 NMR spectra . . . 198
2.15.5.3 Mass spectra . . . 200
2.15.6 Molecular structures . . . 201
2.16 Coordination of the (µ-S) ligand to Fe(CO)x (x = 2 or 3) fragments from Fe2(CO)9
2.16.1 The reaction of [CpCr(SBz)]2S with 2 mole equivalent of Fe2(CO)9 . . . 208
2.16.2 The reaction of [CpMo(SBz)(S)]2 with 2 mole equivalent of
Fe2(CO)9 at room temperature. . . . 208
2.16.3 Physical properties . . . 209
2.16.4 Spectral characteristics
2.16.4.1 IR spectra . . . 210
2.16.4.2 NMR spectra . . . 211
2.16.4.3 Mass spectra . . . 212
2.16.5 Molecular structures . . . 213
2.17 The Reaction of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) with [CpCr(CO)3]2 (1)
2.17.1 The Reaction of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) with one mole
equivalent of [CpCr(CO)3]2 (1) at 110 °C . . . 221
2.17.2 Physical properties . . . 224
2.17.3 Spectra characteristics
2.17.3.1 IR spectrum . . . 224
2.17.3.2 NMR spectrum . . . 224
xix
2.17.3.3 Mass spectrum . . . 224
2.17.4 Molecular structures . . . 225
2.18 Conclusions . . . 229
CHAPTER III EXPERIMENTAL
3.1 General Procedures . . . 230
3.1.1 Physical measurements . . . 230
3.1.2 Solvents and reagents . . . 231
3.2 Preparation of starting complexes
3.2.1 Preparation of Dicyclopentadienylhexacarbonyldichromium
and Dicyclopentadienylhexacarbonyldimolybdenum,
[CpM(CO)3]2 [M = Cr(1) or Mo(2)] . . . 232
3.2.2 Preparation of Dicyclopentadienyltetracarbonyldichromium,
[CpCr(CO)2]2 . . . 233
3.2.3 Preparation of Dicyclopentadienyltetracarbonyldimolybdenum,
[CpMo(CO)2]2 . . . 233
3.2.4 Preparation of Tris(o-thiomethylphenyl)phosphine, o-P(PhSMe)3 . . . 233
3.2.5 Synthesis of Bis(o-thiomethylphenyl)phenylphosphine,
PPh(C6H4SMe-o)2 . . . 234
3.2.6 Synthesis of (o-Thiomethylphenyl)diphenyl phosphine,
PPh2(C6H4SMe-o) . . . 235
3.2.7 Preparation of Tris(p-thiomethylphenyl)phosphine, P(C6H4SMe-p)3. . . 235
3.2.8 Preparation of Diiron Enneacarbonyl, Fe2(CO)9 . . . 236
3.3 Reactions of [CpCr(CO)3]2 with Bibenzyl Trisulfide, Bz2S3
3.3.1 Reactivity studies of [CpCr(CO)3]2 with an equimolar of
Bibenzyl Trisulfide at ambient temperature . . . 237
3.3.2 Reactivity studies of [CpCr(CO)3]2 with an equimolar of
Bibenzyl Trisulfide at 60 °C . . . 238
xx
3.3.3 Reactivity studies of [CpCr(CO)2]2 with an equimolar of
Bibenzyl Trisulfide at ambient temperature . . . 238
3.3.4 Thermolysis of [CpCr(CO)2(SBz)]2 (6) . . . 239
3.3.5 Thermolysis of [CpCr(SBz)]2S (7) . . . 239
3.3.6 NMR Tube Reactions . . . 239
3.4 Reaction Of [CpMo(CO)3]2 With Bibenzyl Trisulfide
3.4.1 Reactivity studies of [CpMo(CO)3]2 with an equimolar
of Bibenzyl Trisulfide at 60 °C . . . 240
3.4.2 Thermolysis of [CpMo(CO)2(SBz)]2 (9) . . . 242
3.4.3 Thermolysis of [CpMo(CO)(SBz)]2S (11) . . . 242
3.4.4 NMR tube reactions . . . 243
3.5 Reactions of [CpCr(CO)3]2 with Bibenzyl Disulfide
3.5.1 Reactivity studies of [CpCr(CO)3]2 with an equimolar of
Bibenzyl Disulfide at ambient temperature . . . 243
3.5.2 Reactivity studies of [CpCr(CO)3]2 with an equimolar of
Bibenzyl Disulfide at 110 ˚C . . . 244
3.5.3 Reactivity studies of [CpCr(CO)2]2 with an equimolar of
Bibenzyl Disulfide at 110 ˚C . . . 245
3.5.4 NMR Tube Reaction . . . 246
3.6 Reactions of [CpMo(CO)2]2 with Bibenzyl Disulfide
3.6.1 Reactivity studies of [CpMo(CO)2]2 with an equimolar
of Bibenzyl Disulfide at 70 °C . . . 247
3.6.2 Reactivity studies of [CpMo(CO)2]2 with an equimolar of
Bibenzyl Disulfide at 110 °C . . . 248
3.6.3 Solventless reaction at 110 °C for 2 h . . . 249
3.6.4 Cothermolysis reaction of trans-syn[CpMo(CO)(SBz)]2 (12a)
with an equimolar of Bz2S2 at 110 °C for 2 h . . . 250
xxi
3.6.5 NMR Tube Reactions . . . 251
3.7 Reaction of [CpMo(CO)3]2 with Davy’s reagent
3.7.1 Reaction of [CpMo(CO)3]2 with equimolar Davy’s reagent at
110 oC . . . 252
3.7.2 Reaction of [CpMo(CO)2]2 with equilmolar Davy’s reagent at
70 °C . . . 253
3.7.3 Reaction of [CpMo(CO)2]2 with 0.5 mole equivalent
Davy’s reagent at 110 °C . . . 254
3.7.4 Reaction of [CpMo(CO)2]2 with 0.5 mole equivalent of
Davy’s reagent at 70 °C . . . 256
3.7.5 NMR Tube Reactions . . . 257
3.8 Reaction of Cp2Cr2(CO)6 with Woollins’ reagent
3.8.1 Reactivity studies of Cp2Cr2(CO)6 (1) with equimolar
Woollins’ reagent at ambient temperature . . . 260
3.8.2 Reaction of excess Cp2Cr2(CO)6 (1) with Woollins’ Reagent
at ambient temperature . . . 261
3.8.3 Reaction of Cp2Cr2(CO)4 (2) with equimolar Woollins’ reagent
at 60 °C . . . 262
3.8.4 NMR tube reactions . . . 263
3.9 Reaction of Cp2Mo2(CO)4 with Woollins’ reagent
3.9.1 Reactivity studies of Cp2Mo2(CO)4 with equimolar
Woollins’ reagent at 110 °C . . . 264
3.9.2 Reactivity studies of Cp2Mo2(CO)4 with equimolar
Woollins’ reagent at 60 °C . . . 267
3.9.3 NMR Tube Reaction . . . 268
3.10 Reaction of Cp2Cr2(CO)6 with P(C6H4SMe-p)3
3.10.1 Reaction of Cp2Cr2(CO)6 with one mole equivalent of
xxii
P(C6H4SMe-p)3 at 70 °C . . . 268
3.10.2 Reaction of Cp2Cr2(CO)4 with one mole equivalent of
P(C6H4SMe-p)3 at 110 °C . . . 269
3.11 Reactions of Cp2Mo2(CO)6 with P(C6H4SMe-p)3
3.11.1 Reaction of Cp2Mo2(CO)6 with one mole equivalent of
P(C6H4SMe-p)3 at 70 °C . . . 270
3.11.2 Reaction of Cp2Mo2(CO)4 with one mole equivalent of
P(C6H4SMe-p)3 at 110 °C . . . 270
3.12 Reaction of Cp2Cr2(CO)6 with PPh2(C6H4SMe-o)
3.12.1 Reaction of Cp2Cr2(CO)6 with 2.5 mole equivalent of
PPh2(C6H4SMe-o) at 60 °C . . . 272
3.12.2 NMR tube reaction . . . 273
3.13 Reaction of Cp2Cr2(CO)6 with PPh(C6H4SMe-o)2
3.13.1 Reaction of Cp2Cr2(CO)6 with one mole equivalent of
PPh(C6H4SMe-o)2 at 110 °C . . . 273
3.13.2 Reaction of Cp2Cr2(CO)4 with one mole equivalent of
PPh(C6H4SMe-o)2 at 110 °C . . . 274
3.13.3 NMR Tube Reaction . . . 275
3.14 Reaction of Cp2Cr2(CO)6 with P(C6H4SMe-o)3
3.14.1 Reaction of Cp2Cr2(CO)6 with one mole equivalent of
P(C6H4SMe-o)3 at 110 °C . . . 276
3.14.2 Reaction of Cp2Cr2(CO)4 with one mole equivalent of
P(C6H4SMe-o)3 at 110 °C . . . 277
3.14.3 NMR tube reaction . . . 277
3.15 Reactivity studies of Cp2Mo2(CO)4 with PPh2(C6H4SMe-o)
3.15.1 Reaction of Cp2Mo2(CO)4 with one mole equivalent of
PPh2(C6H4SMe-o) at 110 °C . . . 278
xxiii
3.16 Reactivity studies of Cp2Mo2(CO)4 with PPh(C6H4SMe-o)2
3.16.1 Reaction of Cp2Mo2(CO)4 with one mole equivalent of
PPh(C6H4SMe-o)2 at 110 °C . . . 279
3.16.2 NMR tube reaction . . . 280
3.17 Reaction of Cp2Mo2(CO)4 with P(C6H4SMe-o)3
3.17.1 Reaction of Cp2Mo2(CO)4 with one mole equivalent of
P(C6H4SMe-o)3 at 110 °C . . . 280
3.17.2 NMR tube reactions . . . 283
3.18 Formation of specific transition metal carbonyl fragments adducts of
[CpM(SBz)]2Sn (M = Cr, n =1 or Mo, n = 2)
3.18.1 Reaction of [CpCr(SBz)]2S with 2 mole equivalent of Fe2(CO)9 . . . 283
3.18.2 Reaction of [CpMo(SBz)(S)]2 with 2 mole equivalent of
Fe2(CO)9 at room temperature . . . 284
3.19 Reaction of [CpMo(CO)2(S2P(SC6H4Me)2)] (14) with one mole
equivalent of [CpCr(CO)3]2 (1) at 110 °C . . . 285
3.20 Structure determinations . . . 287
3.21 R.F. values of complexes . . . 323
REFERENCES . . . 326
APPENDIX I . . . 335
APPENDIX II . . . 374
xxiv
LIST OF FIGURES
Page
Figure 1. Molecular structure of [CpMo(CO)2(µ-SPh)]2 . . . 8
Figure 2. Molecular structure of [CpMo(CO)(µ-SBut)]2 . . . 9
Figure 3. Molecular structure of [CpMo(CO)2(µ-SePh)]2 . . . 10
Figure 4. Molecular structure of [CpMo(µ-Se)(µ-SePh)] . . . 10
Figure 5. Molecular structure of trans/anti-[(η5-MeCOC5H4)Mo(CO)(µ-SPh)]2 . . . 12
Figure 6. Molecular structure of trans/syn-[(η5-MeCOC5H4)Mo(CO)(µ-SPh)]2 . . . 12
Figure 7. The proposed initial step in the P-P and S-S bond cleavage reaction
with 4 . . . 24
Figure 8. Molecular structure of Cp4Cr4(CO)9(P4S3) . . . 25
Figure 9. Molecular structure of Cp4Cr4(CO)9(P4Se3) . . . 26
Figure 10. Molecular structure of [CpCr(CO)2(SBz)]2 (6) . . . 44
Figure 11. Molecular structure of [CpMo(CO)2(SBz)]2 (9) . . . 52
Figure 12. Molecular structure of the orthorhombic modification of
[CpMo(S)(SBz)]2 (10a) . . . 55
Figure 13. Molecular structure of the monoclinic modification of
[CpMo(SBz)S]2 (10b) . . . 56
Figure 14. Molecular structure of [CpMo(CO)(SBz)]2S (11) . . . 57
Figure 15. Molecular structure of [CpCr(SBz)]2S (7) . . . 65
Figure 16. Time-dependant 1H NMR spectra changes of trans-anti[CpMo(CO)(SBz)]2
(12b) in benzene-d6 at 110 °C . . . 69
Figure 17. Time-dependant 1H NMR spectra changes of cothermolysis of trans-syn
[CpMo(CO)(SBz)]2 (12a) with 1 mole equivalent of Bz2S2 at 110 °C . . . 72
Figure 18. Molecular structure of trans-anti [CpMo(CO)(SBz)]2 (12b) . . . 78
Figure 19. Molecular structure of [CpMo(SBz)2]2 (13) . . . 80
Figure 20. Molecular structure of CpMo(CO)2{S2P(SC6H4Me)2} (14) . . . 100
xxv
Figure 21. Molecular structure of Cp2Mo2(CO)5{S2P(SC6H4Me)} (15) . . . 101
Figure 22. Molecular structure of Cp2Mo2(µ-S2)(µ-S)(µ-SC6H4Me) (16) . . . 102
Figure 23. Molecular structure of Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me) (18) . . . 104
Figure 24. Molecular structure of Cp3Mo3(µ-S)2(µ-S2)(µ3-S) (20) . . . 106
Figure 25. Molecular structure of trans-[CpCr(CO)2(SePPh)]2 (22) . . . 119
Figure 26. Molecular structure of CpCr(CO)2(SeP(H)Ph) (23) . . . 121
Figure 27. Molecular structure of [CpCr(Se2P(O)Ph)]2 (24) . . . 123
Figure 28. 31
P NMR decouple spectrum of [Cp2Mo2{(µ-Se)2(PPh(Se))}{(µ-Se)(PPh)3}]
(25) measure in ppm . . . 132
Figure 29. 31
P NMR decouple spectrum of [Cp2Mo2{(µ-Se)2(PPh(Se))}{(µ-Se)(PPh)3}]
(25) measure in KHz . . . 133
Figure 30. Temperature-dependent 1H NMR spectra of Cp4Mo4(CO)3Se4 (26)
in toluene-d8 . . . 134
Figure 31. Molecular structure of [Cp2Mo2{(µ-Se)2(PPh(Se))}{(µ-Se)(PPh)3}] (25). . . 137
Figure 32. Molecular structure of Cp4Mo4(CO)3Se4 (26) . . . 139
Figure 33. Molecular structure of Cp3Mo3(CO)4[Se3(PPh)2] (27a) . . . 142
Figure 34. Molecular structure of Cp2Mo2(CO)5{P(C6H4SMe-p)3} (29) . . . 154
Figure 35. Molecular structure of Cp2Mo2(CO)(µ-CO)2{P(C6H4SMe-p)3} (30) . . . 156
Figure 36. Molecular structure of Cp4Mo4(CO)4(µ3-O)(µ2-O)2(O) (31) . . . 158
Figure 37. Molecular structure of CpCr(CO)2{o-(SC6H4)PPh2} (32) . . . 164
Figure 38. Time-dependant 1H NMR spectra of [CpCr(CO)3]2 (1) with one mole
equivalent of PPh(C6H4SMe-o)2 at 110 °C . . . 168
Figure 39. Molecular structure of [Cp2Cr2(CO){(µ-SC6H4)2PPh}] (33) . . . 171
Figure 40. Molecular structure of CpCr{(µ-SC6H4)2PPh} (34) . . . 172
Figure 41. Time-dependant 1H NMR spectra of [CpCr(CO)3]2 (1) with one mole
equivalent of P(C6H4SMe-o)3 at 80 °C . . . 175
xxvi
Figure 42. Molecular structure of [Cp2Cr2(CO){(µ-SC6H4)2(C6H4SMe-o)P}] (35) . . . 178
Figure 43. Molecular structure of CpMo(CO)2{o-(SC6H4)PPh2} (36) . . . 182
Figure 44. Molecular structure of [Cp2Mo2(CO){(µ-SC6H4)2PPh}] (38) . . . 190
Figure 45. Molecular structure of CpMo(CO){(µ-SC6H4)(µ-SMePh)PPh} (39) . . . 191
Figure 46. Molecular structure of [Cp2Mo2(CO){(µ-SC6H4)2(o-PhSCH2)P}] (40) . . . 201
Figure 47. Molecular structure of [Cp2Mo2(CO){(µ-SC6H4)2(C6H4SMe-o)P}] (41) . . . 202
Figure 48. Molecular structure of Mo(CO)3{P(C6H4SMe-o)3} (42) . . . 204
Figure 49. Molecular structure of CpMo2(CO)3(µ-S){(µ-SC6H4)2(C6H4SMe-o)P}(43). .206
Figure 50. Molecular structure of [Cp2Cr2(SBz)]S2[Fe(CO)3] (44) . . . 213
Figure 51. Molecular structure of [CpMo]2S4[Fe(CO)3]2 (45) . . . 215
Figure 52. Molecular structure of [CpMo]2S3[Fe(CO)3]2 (46) . . . 217
Figure 53. Molecular structure of [CpMo(SBz)]2S2[Fe(CO)2] (47) . . . 219
Figure 54. Molecular structure of [CpMo(CO)2(µ-S)]2 (19) . . . 225
Figure 55. Molecular structure of [CpCr(µ-SC6H4Me)]2S (48) . . . 227
xxvii
LIST OF TABLES
Page
Table 1. Variation of product composition
a from the reaction of
[CpCr(CO)2 ]2S (5) with Bz2S3 at 60 °C . . . 38
Table 2. Electrospray ionization mass spectrum of [CpCr(CO)2(SBz)]2 (6) . . . 43
Table 3. Electrospray ionization mass spectrum of [CpCr(SBz)]2S (7) . . . 43
Table 4. Bond lengths [Å] and angles [°] for [CpCr(CO)2(SBz)]2 (6) . . . 45
Table 5. Variation of product compositiona from the reaction of
[CpMo(CO)2(SBz)]2 (9) with Bz2S3 at 60 °C . . . 47
Table 6. Bond lengths [Å] and angles [deg] for [CpMo(CO)2(SBz)]2 (9) . . . 53
Table 7. Comparison of Mo-Mo bonds and Mo-S bonds . . . 54
Table 8. Bond lengths (Å) and angles (º) for 10a and 10b . . . 56
Table 9. Bond lengths [A] and angles [deg] for [CpMo(CO)(SBz)]2S (11) . . . 58
Table 10. Variation of product compositiona from the reaction of
[CpCr(CO)2 ]2 (2) with Bz2S2 at 60 °C . . . 60
Table 11. Dissociation energies of polysulfide . . . 62
Table 12. Bond lengths [Å] and angles [°] for [CpCr(SBz)]2S (7) . . . 66
Table 13. Time dependent variation of product compositiona from thermolysis
study of trans-anti [CpMo(CO)(SBz)]2 (12b) . . . 68
Table 14. Electrospray ionization mass spectrum of [CpMo(CO)(SBz)]2 (12b) . . . 77
Table 15. Bond lengths [Å] and angles [deg] for trans-anti[CpMo(CO)(SBz)]2 (12b) . . 79
Table 16. Bond lengths [Å] and angles [deg] for [CpMo(SBz)2]2 (13) . . . 81
Table 17. Electrospray ionization mass spectrum of CpMo(CO)2{S2P(SC6H4Me)2} (14)
. . . 97
Table 18. Electrospray ionization mass spectrum of [Cp2Mo2(CO)5(SP(SC6H4Me))] (15)
. . . 97
Table 19. Electrospray ionization mass spectrum of Cp2Mo2(µ-S2)(µ-S)(µ-SC6H4Me) (16)
. . . 98
xxviii
Table 20. Electrospray ionization mass spectrum of [CpMo(CO)(SC6H4Me)]2 (17a) . . . 98
Table 21. Electrospray ionization mass spectrum of Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me) (18)
. . . 99
Table 22. Electrospray ionization mass spectrum of [CpMo(CO)2S]2 (19) . . . 99
Table 23. Electrospray ionization mass spectrum of Cp3Mo3(µ-S)2(µ-S2)(µ3-S) (20). . . 100
Table 24. Bond lengths (Å) and angles (o) for 14, 15 and 16 . . . 103
Table 25. Bond lengths [Å] and angles [°] for Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me) (18)
. . . 105
Table 26. Bond lengths [Å] and angles [°] for Cp3Mo3(µ-S)2(µ-S2)(µ3-S) (20) . . . 107
Table 27. Time dependent variation of product compositiona from thermolysis
study of CpCr(CO)2(SeP(H)Ph) (23) . . . 110
Table 28. Time dependent variation of product compositiona from the thermolysis
study of trans-[CpCr(CO)2(SePPh)]2 (22) . . . 111
Table 29. Time dependent variation of product compositiona from cothermolysis
study of CpCr(CO)2(SeP(H)Ph) (23) with Woollins’ reagent . . . 112
Table 30. Electrospray ionization mass spectrum of trans-[CpCr(CO)2(SePPh)]2 (22). . 117
Table 31. Electrospray ionization mass spectrum of CpCr(CO)2(SeP(H)Ph) (23) . . . 118
Table 32. Electrospray ionization mass spectrum of [CpCr(Se2P(O)Ph)]2 (24) . . . 118
Table 33. Bond lengths [Å] and angles [°] for trans-[CpCr(CO)2(SePPh)]2 (22) . . . 120
Table 34. Bond lengths [Å] and angles [°] for CpCr(CO)2(SeP(H)Ph) (23) . . . 122
Table 35. Bond lengths [Å] and angles [°] for [CpCr(Se2P(O)Ph)]2 (24) . . . 124
Table 36. 31
P{1H} NMR Resonances of [Cp2Mo2{(µ-Se)2(PPh(Se))}
{(µ-Se)(PPh)3}] (25) . . . 130
Table 37. Electrospray ionization mass spectrum of [Cp2Mo2{(µ-Se)2(PPh(Se))}
{(µ-Se)(PPh)3}] (25) . . . 136
Table 38. Electrospray ionization mass spectrum of Cp4Mo4(CO)3Se4 (26) . . . 136
Table 39. Electrospray ionization mass spectrum of Cp3Mo3(CO)4[Se3(PPh)2] (27) . . . 137
xxix
Table 40. Bond lengths [Å] and angles [°] for [Cp2Mo2{(µ-Se)2(PPh(Se))}{(µ-Se)(PPh)3}] (25)
. . . 138
Table 41. Bond lengths [Å] and angles [°] for Cp4Mo4(CO)3Se4 (26) . . . 140
Table 42. Bond lengths [Å] and angles [°] for Cp3Mo3(CO)4[Se3(PPh)2] (27a) . . . 143
Table 43. Electrospray ionization mass spectrum of [CpCr(CO)2{P(C6H4SMe)3}2]-
[CpCr(CO)3] (28) . . . 147
Table 44. Electrospray ionization mass spectrum of Cp2Mo2(CO)5{P(SC6H4-p)3}(29). .153
Table 45. Electrospray ionization mass spectrum of Cp2Mo2(CO)(µ-CO)2{P(SC6H4-
p)3}(30) . . . 153
Table 46. Bond lengths [Å] and angles [°] for Cp2Mo2(CO)5{P(SC6H4-p)3} (29) . . . 155
Table 47. Bond lengths [Å] and angles [°] for Cp2Mo2(CO)(µ-CO)2{P(SC6H4-p)3} (30)
. . . 157
Table 48. Bond lengths [Å] and angles [°] for Cp4Mo4(CO)4(µ3-O)(µ2-O)2(O) (31) . . . 159
Table 49. Electrospray ionization mass spectrum of CpCr(CO)2{o-(SC6H4)PPh2} (32) . 163
Table 50. Bond lengths [Å] and angles [°] for CpCr(CO)2{o-(SC6H4)PPh2} (32) . . . 165
Table 51. Electrospray ionization mass spectrum of
[Cp2Cr2(CO){(µ-SC6H4)2PPh}] (33) . . . 170
Table 52. Bond lengths [Å] and bond angles [°] for complex 33 . . . 172
Table 53. Bond lengths [Å] and bond angles [°] for complex CpCr{(µ-SC6H4)2PPh}(34)
. . . 173
Table 54. Electrospray ionization mass spectrum of [Cp2Cr2(CO){(µ-SC6H4)2-
(SC6H4-o)P}] (35) . . . 178
Table 55. Bond lengths [Å] and angles [°] for [Cp2Cr2(CO){(µ-SC6H4)2-
(SC6H4-o)P}] (35) . . . 179
Table 56. Electrospray ionization mass spectrum of CpMo(CO)2{o-(SC6H4)PPh2} (36)
. . . 182
Table 57. Bond lengths [Å)] and angles [º] for CpMo(CO)2{o-(SC6H4)PPh2} (36) . . . 183
Table 58. Electrospray ionization mass spectrum of [Cp2Mo2(CO){(µ-SC6H4)2PPh}] (38)
. . . 189
Table 59. Electrospray ionization mass spectrum of CpMo(CO){(µ-SC6H4)-
xxx
(µ-C6H4SMe)PPh}(39) . . . 189
Table 60. Bond lengths [Å] and angles [°] for [Cp2Mo2(CO){(µ-SC6H4)2PPh}] (38) . . .191
Table 61. Bond lengths [Å] and angles [°] for CpMo(CO){(µ-SC6H4)(µ-
C6H4SMe)PPh}(39) . . . 192
Table 62. Electrospray ionization mass spectrum of [Cp2Mo2(CO){(µ-SC6H4)2-
(C6H4SMe-o)P}] (41) . . . 200
Table 63. Electrospray ionization mass spectrum of Mo(CO)3{o-P(SC6H4Me-o)3}(42). 200
Table 64. Bond lengths [Å] and angles [°] for [Cp2Mo2(CO){(µ-SC6H4)2(PhSCH2-o)P}]
(40) . . . 202
Table 65. Bond lengths [Å] and angles [°] for [Cp2Mo2(CO){(µ-SC6H4)2(SC6H4Me-o)P}]
(41) . . . 203
Table 66. Bond lengths [Å] and angles [°] for Mo(CO)3{P(SC6H4Me-o)3} (42) . . . 205
Table 67. Bond lengths [Å] and angles [°] for CpMo2(CO)3(µ-S){(µ-SC6H4)2(o-
SMe)P}(43) . . . 207
Table 68. Electrospray ionization mass spectrum of [Cp2Cr2(SBz)]S2[Fe(CO)3] (44) . . 212
Table 69. Electrospray ionization mass spectrum of [CpMo(SBz)]2S2[Fe(CO)2] (47) . . 212
Table 70. Bond lengths [Å] and angles [°] for [Cp2Cr2(SBz)]S2[Fe(CO)3] (44) . . . 214
Table 71. Bond lengths [Å] and angles [°] for [CpMo]2S4[Fe(CO)3]2 (45) . . . 216
Table 72. Bond lengths [Å] and angles [°] for [CpMo]2S3[Fe(CO)3]2 (46) . . . 218
Table 73. Bond lengths [Å] and angles [°] for [CpMo(SBz)]2S2[Fe(CO)2] (47) . . . 220
Table 74. Bond lengths [Å] and angles [°] for [CpMo(CO)2(µ-S)]2 (19) . . . 226
Table 75. Bond lengths [Å] and angles [°] for [CpCr(µ-SC6H4Me)]2S (48) . . . 227
Table 76. Crystal data and structure refinement for [CpCr(CO)2(SBz)]2 (6) . . . 290
Table 77. Crystal data and structure refinement for [CpCr(SBz)]2S (7) . . . 291
Table 78. Crystal data and structure refinement for [CpMo(CO)2(SBz)]2 (9) and
[CpMo(CO)(SBz)]2S (11) . . . 293
Table 79. Crystals data and structure refinement for [CpMo(SBz)(S)]2 (10a & b) . . . 294
xxxi
Table 80. Crystals data and structure refinement for trans-anti[CpMo(CO)(SBz)]2 (12b)
and [CpMo(SBz)2]2 (13) . . . 296
Table 81. Data collection and processing parameters of CpMo(CO)2{S2P(SC6H4Me)2}(14),
Cp2Mo2(CO)5{S2P(SC6H4Me)} (15) and Cp2Mo2(µ-S2)(µ-S)(µ-SC6H4Me) (16)
. . . 298
Table 82. Data collection and processing parameters of Cp2Mo2(CO)2(µ-PS)(µ-SC6H4Me)
(18) and Cp3Mo3(µ-S)2(µ-S2)(µ3-S) (20) . . . 300
Table 83. Data collection and processing parameters of trans-[CpCr(CO)2(SePPh)]2 (22),
CpCr(CO)2(SeP(H)Ph) (23) and Cp2Cr2(Se2P(O)Ph)2 (24) . . . 302
Table 84. Data collection and processing parameters of [Cp2Mo2{(µ-Se)2(PPh(Se))}
{(µ-Se)(PPh)3}] (25), Cp4Mo4(CO)3Se4 (26) and Cp3Mo3(CO)4[Se3(PPh)2] (27)
. . . 304
Table 85. Data collection and processing parameters of Cp2Mo2(CO)5{P(SC6H4Me-p)3}
(29), Cp2Mo2(CO)(µ-CO)2{P(SC6H4Me-p)3} (30) and Cp4Mo4(CO)4(µ3-O)(µ2-
O)2(O) (31) . . . 306
Table 86. Data collection and processing parameters of CpCr(CO)2{o-(SC6H4)PPh2} (32)
. . . 308
Table 87. Data collection and processing parameters of [Cp2Cr2(CO){(µ-SC6H4)2PPh}]
(33) and CpCr{(µ-SC6H4)2PPh} (34) . . . 310
Table 88. Data collection and processing parameters of [Cp2Cr2(CO){(µ-SC6H4)2-
(SC6H4Me-o)P}] (35) . . . 312
Table 89. Data collection and processing parameters of CpMo(CO)2{o-(SC6H4)PPh2} (36)
. . . 314
Table 90. Data collection and processing parameters of [Cp2Mo2(CO){(µ-SC6H4)2PPh}]
(38) and CpMo(CO){(µ-SC6H4)(µ-SC6H4Me)PPh} (39) . . . 316
Table 91. Data collection and processing parameters of [Cp2Mo2(CO){(µ-SC6H4)2-
(PhSCH2-o)P}] (40) and [Cp2Mo2(CO){(µ-SC6H4)2(SC6H4Me-o)P}] (41). . .318
Table 92. Data collection and processing parameters of Mo(CO)3{P(SC6H4Me-o)3} (42)
and CpMo2(CO)3(µ-S){(µ-SC6H4)( SC6H4Me-o)P}(43) . . . 319
Table 93. Data collection and processing parameters of [Cp2Cr2(SBz)]S2[Fe(CO)3] (44)
. . . 321
Table 94. Data collection and processing parameters of [CpMo]2S4[Fe(CO)3]2 (45),
[CpMo]2S3[Fe(CO)3]2 (46) and [CpMo(SBz)]2S2[Fe(CO)2] (47) . . . 323
xxxii
Table 95. Data collection and processing parameters of [CpMo(CO)2(µ-S)]2 (19) and
[CpCr(µ-SC6H4Me)]2S (47) . . . 325
Table 96. R.F. values of complexes . . . 326
xxxiii
LIST OF ABBREVIATIONS
e- Electron
σ Sigma
π Pi
λ Lambda (wavelength)
δ PPM
Ar Aromatic ring
Bz Benzyl
But tert-Butyl
Cp Cyclopentadienyl
Cp* Pentamethylcyclopentadienyl
Cp’ Methylcyclopentadienyl
Cp’’ Ethyltetramethylcyclopentadienyl
C6D6 Deuterated benzene-d6
C6D5CD3 Deuterated toluene-d8
Cosy Correlation spectroscopy
dppe 1,2-Bis(diphenylphosphino)ethane
Eqn Equation
ESI Electrospray ionization
Et Ethyl
h Hour
HMBC Hetero-nuclear multiple-bond connectivity
HMQC Hetero-nuclear multiple quantum coherence
IR Infrared spectroscopy
xxxiv
J Coupling constant
Me Methyl
LCMS Liquid chromatography mass spectrometry
Ph Phenyl
PBu3 Tributylphosphine
PEt3 Triethylphosphine
PMe2Ph Dimethylphenylphosphine
PPh2Me Diphenylmethylphosphine
PPh3 Triphenylphosphine
P(OBu)3 Tributoxyphosphine
P(OPh)3 Triphenoxyphosphine
iPr Isopropyl
THF Tetrahydrofuran
TLC Thin layer chromatography
UV Ultraviolet