عنوان

Reactions of ruthenium and platinum thiolates and the development of novel homogeneous catalysts of Claus chemistry

Number

TLpq250116304

.Language of Text, Soundtrack etc

انگلیسی

Title Proper

Reactions of ruthenium and platinum thiolates and the development of novel homogeneous catalysts of Claus chemistry

General Material Designation

[Thesis]

First Statement of Responsibility

M. El-khateeb

Subsequent Statement of Responsibility

A. Shaver

Name of Publisher, Distributor, etc.

McGill University (Canada)

Date of Publication, Distribution, etc.

1996

Specific Material Designation and Extent of Item

204

Dissertation or thesis details and type of degree

Ph.D.

Body granting the degree

McGill University (Canada)

Text preceding or following the note

1996

Text of Note

The complexes CpRu(PPh3)(L)SR (Cp=usd\eta\sp5usd-cyclopentadienyl; R=CMe3, CHMe2, 4-usd\rm C\sb6H\sb4Me)usd reacted with NOBF4 to give either (CpRu(PPh3)(NO)SR) BF4 (L=PPh3) or complexes containing disulfide ligands (L=CO). The bisphosphine complexes, CpRu(PPh3)\sb2SR, reacted with HBF4 to give the corresponding thiol complex salts (CpRu(PPh3)\sb2(HSR)) BF4 and with (MeSSMEusd\rm\sb2\rbrack BF\sb4usd to give (CpRu(PPh3)\sb2(SMe2)) BF4 regardless of the starting thiolates. The complexes CpRu(PPh3)\sb2SR reacted with the sulfur transfer agent MeSphth (phth=phthalimido) to give CpRu (PPh3)\sb2(phth) and the dimers (mu-SMe)(mu-SR) (CpRu(phth)) 2 for R=CMe3 or CHMe2, while for R=4-usd\rm C\sb6H\sb4Meusd the same reaction gave CpRu(PPh3)(phth)(MeSS-4-usd\rm C\sb6H\sb4Me)usd and (mu-SMe)(mu-S-4-usd\rm C\sb6H\sb4usdMe) (CpRu(S-4-usd\rm C\sb6H\sb4Me)\rbrack\sb2.usd The complex CpRu(PPh3)\sb2 SCH2CH=CH2, prepared from the reaction of CpRu(PPh3)\sb2Cl and LiSCH2CH=CH2, reacted with CO and CS2 to give CpRu(PPh3)(CO)SCH2CH=CH2 and CpRu(PPh3)S2CSCH2CH=CH2, respectively. Refluxing a toluene solution of CpRu(PPh3)\sb2SCH2CH=CH2 gave (usd\mu\sb3usd-S)2(\mu-SCH2CH=CH2) (CpRu) 3 in which the C-S bond has been cleaved. The complexes (PPh3)\sb2Pt(SR)2 (R=H, usd\rm CMe\sb3,\ CHMe\sb2,usd 4-usd\rm C\sb6H\sb4Me)usd were treated with SO2 as models for the Claus process. These reactions produced adducts of formula (PPh3)\sb2Pt(S(SO2)R)2, which have a labile thiolate-bound SO2 molecule, for R=CMe3, 4-usd\rm C\sb6H\sb4Meusd and CHMe2. The reaction of cis-(PPh3)\sb2Pt(SH)2 with SO2 gave (PPh3)\sb2Pt(S3O) and H2O, a reaction which mimics Claus chemistry. The complexes cis-(PPh3)\sb2Pt(SH)2, (PPh3)\sb2Pt(S3O) and (PPh3)\sb2Pt(SR)2 catalyze the Claus reaction (2H2S + SOusd\rm\sb2\to3/8S\sb8+2H\sb2O).usd The complexes (PPh3)\sb2Pt(SR)2 reacted with CS2 to form the mixed thiolato-thioxanthato complexes (PPh3)Pt(SR)(S2CSR) wherein CS2 had inserted into one of the Pt-S bonds. The complex cis-(PPh3)\sb2Pt(SH)2 reacted with CS2 to give the known complex, (PPh3)\sb2Pt(S2CS), which contains a trithiocarbonate group. The structures of (CpRu(PPh3)(NO)SCMeusd\rm\sb3\rbrack BF\sb4,\ (\muusd-SMe)(mu-S-4-usd\rm C\sb6H\sb4Me)usd (CpRu(S-4-usd\rm C\sb6H\sb4Me)\rbrack\sb2,\ (\mu\sb3usd-S)2(\mu-SCH2CH=CH2) (CpRu) 3, (PPh3)\sb2Pt(S3O) and (PPh3)Pt(S-4-usd\rm C\sb6H\sb4Me)usd(S2CS-4-usd\rm C\sb6H\sb4Me)usd were determined by x-ray crystallography.

Chemistry

Pure sciences

A. Shaver

M. El-khateeb

Electronic name

p

[Thesis]

276903

a

Y