Reactions of the molybdenum bis(alkyne) complex [mo(SC6F5)(F3CC≡CCF3) 25-C5H5)] with alkynes leading to isomeric and fluxional η4-butadienyl complexes

Naz M. Agh-Atabay, Jack L. Davidson

Research output: Contribution to journalArticle

Abstract

Reactions of the bis(hexafluorobut-2-yne) complex [Mo(SC6F5)(F3CC=CCF3) 2(?5-C5H5)] 1 with alkynes RC=CR' give the novel ?4-butadienyl complex prone-[Mo{?4-C(CF3)C(CF3)=CRCR(SC 6F5)}(F3CC=CCF3)(? 5-C5H5)] 2 (R = R' = Me; R = H, R' = Me or Ph; R = Me, R' = CO2Me) which undergoes isomerisation via an ?2-C,C vinyl intermediate [Mo{?3-C(CF3)C(CF3)CR=CR'(SC 6F5)}(F3CC=CCF3)(? 5-C5H5)] 3 (R = R' = Me, Et or Ph; R = Me, R' = Co2Me or Ph; R = H, R' = Ph) to the supine isomer 4 (R = R' = Me or Et; R = Me, R' = CO2Me or Ph; R = H, R' = Me or Ph) followed by a novel 1,4 thiolate migration to give supine-[Mo{?4-CR'CR;C(CF3)C(CF 3)(SC6F5)}(F3CC=CCF 3)(?5-C5H5)] 5 (R = R' = Ph; R = Me, R' = Ph). Fluorine-19 NMR studies established that with PhC=CPh 3 and 5 exist in solution as an equilibrium mixture. With PhC=CMe exchange between 3, 4 and 5 is faster which allowed study by dynamic 19F NMR and spin-saturation-transfer experiments.

Original languageEnglish
Pages (from-to)3531-3539
Number of pages9
JournalJournal of the Chemical Society, Dalton Transactions
Issue number24
DOIs
Publication statusPublished - 1992

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