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Title:The Chemistry of Some Triosmium Alkylidene and Alkylidyne Cluster Complexes
Author(s):Yeh, Wen-Yann
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
Abstract:Upon sequential treatment of ((mu)-H)Os(,3)(CO)(,10)((mu)-COMe) with PhLi and MeOSO(,2)CF(,3), reaction occurs at a carbonyl ligand, affording a mixed alkylidene-alkylidyne complex ((mu)-H)Os(,3)(CO)(,9)((eta)('1)-C(OMe)(,2))((mu)(,3)-CPh), which, on extended treatment with MeOSO(,2)CF(,3) forms the alkylidyne complexes, ((mu)-H)Os(,3)(CO)(,10)((mu)(,3)-CPh) and Os(,3)(CO)(,9)((mu)(,3)-CPh)((mu)(,3)-COMe). These complexes have been characterized by microanalysis and mass, IR, ('1)H and ('13)C NMR spectroscopy together with single-crystal X-ray diffraction analyses.
Further studies of sequential Ph('-)/Me('+) treatment of ((mu)-H)Os(,3)(CO)(,10)((mu)(,3)-CPh), Os(,3)(CO)(,9)((mu)(,3)-CPh)((mu)(,3)-COMe), and ((mu)-H)Os(,3)(CO)(,9)((eta)('1)-C(OMe)(,2))((mu)(,3)-CPh) have demonstrated the effectiveness of this reaction in the transformation of carbonyl ligands to alkylidene and alkylidyne moieties. Moreover, by repeating this two-step procedure, dialkylidyne and mixed alkylidene-alkylidyne complexes can be prepared, although it is difficult to predict the nature of the products.
Several reactions of these complexes have been investigated, such as hydrogenation, pyrolysis, carbonylation, protonation, ligand substitution, and reactivity towards Lewis acids. The stereodynamics of fluxional cluster complexes have been studied by ('1)H and ('13)C NMR spectroscopy. Aspects of the reactivity of alkylidyne and alkylidene ligands have been examined; examples include alkylidyne-alkylidyne coupling with Os(,3)(CO)(,9)((mu)(,3)-CPh)((mu)(,3)-COMe), alkylidyne-carbonyl coupling with ((mu)-H)Os(,3)(CO)(,10)((mu)(,3)-CPh), alkylidyne-alkylidene coupling with ((mu)-H)Os(,3)(CO)(,9)((eta)('1)-C(OMe)(,2))((mu)(,3)-CPh), alkylidyne-alkyne coupling with ((mu)-H)Os(,3)(CO)(,10)((mu)(,3)-CPh), and benzylidyne-tolyne interconversion with ((mu)-H)(,3)Os(,3)(CO)(,9)((mu)(,3)-CPh) and ((mu)-H)(,2)Os(,3)(CO)(,9)((mu)(,3),(eta)('2)-C(,6)H(,3)(CH(,3))).
Issue Date:1986
Type:Text
Description:269 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.
URI:http://hdl.handle.net/2142/70336
Other Identifier(s):(UMI)AAI8623443
Date Available in IDEALS:2014-12-15
Date Deposited:1986


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