Degree Type
Dissertation
Date of Award
1985
Degree Name
Doctor of Philosophy
Department
Chemistry
Abstract
The thiocarbyne cations, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSR)('+) (R = Me, Bz, All), react with a variety of nucleophiles (Nuc = H('-), MeS('-), PHS('-), BzS('-), PhSe('-) and BzMgCl) to give bridging carbene complexes, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SR)Nuc . The cis-syn isomers of (mu)-hydridothiocarbene complexes, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(H)SMe and Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(H)SCH(,2)Ph , have been isolated. In CDCl(,3), these complexes undergo a slow cis-syn to cis-anti interconversion and an even slower cis-syn/trans-syn isomerization. Solutions (in benzene, CHCl(,3), CH(,2)Cl(,2), acetone, and CH(,3)CN) of (mu)-dithiocarbene complexes, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SMe)SR , are equilibrium mixtures of all possible cis and trans isomers. The initially formed (mu)-selenothiocarbene complex, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SMe)SePh , converts to a (mu)-carbyne complex, Cp(,2)Fe(,2)(SePh)(CO)((mu)-CO)((mu)-CSMe), at 0(DEGREES)C. In contrast, the (mu)-dithiocarbene complex, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO) (mu)-C(SMe)SPh , converts to Cp(,2)Fe(,2)(SPh)(CO)((mu)-CO)((mu)-CSMe) at 40(DEGREES)C;Reaction of Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)('+) with primary and secondary amines gives presumably the unstable complexes, CP(,2)Fe(,2)(SMe)(CO)((mu)-CO)((mu)-CNR(,2)). Tertiary amines do not react;A one electron reduction of Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)('+) gives the deep emerald green radical, Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(.), which has been characterized by IR, EPR and UV-visible spectroscopy. Ligand exchange reactions of Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)('+) are catalyzed by the radical, and apparently proceed through a mechanism involving dissociative loss of CO from Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)(.);Reaction of Na Co(CO)(,4) with Cp(,2)Fe(,2)(CO)(,2)((mu)-CO)((mu)-CSMe)('+) under UV photolysis gives Cp(,2)Fe(,2)Co(CO)(,3)((mu)-CO)(,2)((mu)(,3)-CSMe). An x-ray diffraction study of this cluster shows that it has an L-shaped triangular structure, but there is no Co-Fe bond on one edge of the triangle. The CSMe group bonds through the carbyne carbon to all three metals, and in addition the sulfur coordinates to the cobalt atom.
DOI
https://doi.org/10.31274/rtd-180813-6098
Publisher
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Copyright Owner
Norman Clark Schroeder
Copyright Date
1985
Language
en
Proquest ID
AAI8514436
File Format
application/pdf
File Size
304 pages
Recommended Citation
Schroeder, Norman Clark, "Reactivity of bridging thiocarbyne complexes of iron " (1985). Retrospective Theses and Dissertations. 7884.
https://lib.dr.iastate.edu/rtd/7884