Synthesis, structures, and reactions of ethenethiolato complexes of molybdenum and tungsten [M{η3-SC(CF3)=C(CF3)H}(CF 3C≡CCF3)(η5-C5H 5)](M = Mo or W). Their relevance to the mechanism of metal-promoted isomerisation of carbon-carbon double bonds

Naz M. Agh-Atabay, Jack L. Davidson

Research output: Contribution to journalArticle

Abstract

Thermolysis of the ?2-C,C-vinyl complexes [M{?3-C(CF3)C(CF3)SBut}(CF 3C=CCF3)(?5-C5H 5)] (1) (M = Mo or W) gives ?3-ethenethiolato complexes Z-endo-[M{?3-SC(CF3)=C(CF3)H}(CF 3C=CCF3)(?5-C5H 5)] (2). With M = W an intermediato E-exo-[W{?3-SC(CF3)=C(CF3)H}(CF 3C=CCF3)(?5-C5H 5)] (3) was isolated and structurally characterised, illustrating that exo ? endo and E ? Z isomerisations are concomitant processes. The relevance of this observation for mechanism(s) of metal-pormoted alkyne isomerisations is discussed. Reactions of (2) and (3) with tertiary phosphines and dioxygen give s-ethenethiolato complexes [M{SC(CF3)=C(CF3)H}L(CF3C=CCF 3)(?5-C5H5)] (M = Mo, L = O or PPh3; M = W, L = O, PPh3, PMe2Ph, or PPh2C=CPh) with retention of stereochemistry about the C=C bond. Dynamic 19F n.m.r. studies reveal fluxional behaviour in some complexes due to alkyne propeller rotation.

Original languageEnglish
Pages (from-to)1027-1035
Number of pages9
JournalJournal of the Chemical Society, Dalton Transactions
Issue number6
DOIs
Publication statusPublished - 1989

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