Degree Type

Dissertation

Date of Award

1990

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Robert Angelici

Abstract

This dissertation describes the synthesis and reactions of ruthenium- and tungsten-thioalkyne complexes. The alkyne, MeSC≡CSMe, initially reacts with Cp(PMe3)2RuCl to form the sulfur-bound alkyne complex Cp(PMe3)2Ru(S(Me)C≡CSMe) \[superscript]+, which readily rearranges to the vinylidene (Cp(PMe3)2Ru=C=C(SMe)2) [superscript]+. This vinylidene complex is either readily reduced with a variety of charged nucleophiles to give the thioacetylide Cp(PMe3)2Ru-C≡CSMe and MeSSMe; or reacts with electrophiles H[superscript]+ and MeS[superscript]+ (E) to give three-member metallacyclic complexes Cp(PMe3)2Ru(S(Me)C=C(E)SMe) \[superscript]+2. Addition of CuCl or electrophiles H[superscript]+, Me[superscript]+, and MeS[superscript]+ (E) gives the [pi]-bound Cp(PMe3)2Ru(CuCl)(C≡(CSMe) or vinylidene complexes (Cp(PMe3)2Ru=C=C(E)(SMe)) [superscript]+, respectively. Further addition of Me[superscript]+ to a sulfur of (Cp(PMe3)2Ru=C=C(E)(SMe)) [superscript]+ gives the first examples of sulfonium vinylidene dicationic complexes (Cp(PMe3)2Ru=C=C(R)(SMe2)) [superscript]+2. Complexes (Cp(PMe3)2Ru=C=C(Me)(SMe n)) [superscript] +n undergo one- (n = 1) or two-electron (n = 2) reductions to give the acetylide Cp(PMe3)2Ru-C≡CMe and MeSSMe or Me2S, respectively. The reactions of the sulfonium-vinylidene (Cp(PMe3)2Ru=C=C(SMe)(SMe2)) [superscript]+2 with PR3 results in the cleavage of MeS[superscript]+ to form the sulfonium acetylide (Cp(PMe3)2Ru-C≡CSMe2) [superscript]+ and (MeS-Pr3) [superscript]+. This sulfonium-vinylidene complex also reacts with anionic and neutral nucleophiles (Nuc) to yield dicationic vinylidene complexes (Cp(PMe3)2Ru=C=C(Nuc)(SMe)) [superscript]+2 and Me2S;The thioalkyne, MeSC≡CSMe, also reacts with tungsten(II) carbonyl complexes to yield CpW(MeSC≡CSMe)2Cl, W(CO) (MeSC≡CSMe) (S2CNR2)2, and W(MeSC≡CSMe)2(S2CNR2)2. The methyl-sulfonium complexes (CpClW(MeSC≡CSMe) (MeSC≡CSMe2)) [superscript]+ and (CpClW(MeSC≡CSMe) (MeSC≡CS(Me)Ru (PMe3)2Cp)) [superscript]+ are formed by electrophilic addition to a sulfur atom of CpW(MeSC≡CSMe)2Cl. The complex (CpClW(MeSC≡CSMe) (MeSC≡CSMe2)) [superscript]+, which was characterized by X-ray analysis, reacts with anionic nucleophiles H[superscript]- and RS[superscript]- (Nuc) to yield CpW(MeSC≡CSMe) (MeSC≡CNuc)Cl and Me2S.

DOI

https://doi.org/10.31274/rtd-180813-12626

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

David Charles Miller

Language

en

Proquest ID

AAI9035103

File Format

application/pdf

File Size

234 pages

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