Reactions of some iron and tungsten mercapto-complexes with electrophilic acetylenes leading to novel metallacycles. The crystal and molecular structure of the η2-vinyl complex [W{η2-C(CF3)C(CF3)C(O)SMe}(CO)25-C5H5)]

Jack L. Davidson, Mahmoud Shiralian, Ljubica Manojlović-Muir, Kenneth W. Muir

Research output: Contribution to journalArticle

Abstract

Reactions of [Fe(SR')(CO)2(?5-C5H5)] with activated alkynes CF3C=CCF3 and MeO2CC=CCO2Me give heterocyclic complexes [Fe{C(O)C(R)=C(R)SR'}(CO)(?5-C5H5)] (R' = alkyl or aryl, R = CF3 or CO2Me). Related derivatives [W(C(O)C(R)=C(R)SR'}(CO)2(?5-C5H 5)](R' = Me or Et) obtained from [W(SR')(CO)3(?5-C5H5)] and the alkynes in hexane at 20 °C undergo a sequence of thermal isomerisations above 25 °C involving initially a novel 1,3 shift of the SR' ligand across the eneone ligand to give the ?2-vinyl complex [W{?2-C(R)C(R)C(O)SR'}(CO)2(? 5-C5H5)] (R = CF3 only) followed by S-bonded vinyl ketone complexes [W{C(R)=C(R)C(O)SR'}(CO)2(?5-C5H 5)] and ultimately O-bonded vinyl ketone derivatives [W{C(R)=C(R)C(SR')O}(CO)2(?5-C5H 5)] and co-ordinatively unsaturated alkyne complexes [W(SR')(CO)(RC=CR)(?5-C5H5)] (R = CF3 only). An X-ray structure determination of the ?2-vinyl complex [W{?2-C(CF3)C(CF3)C(O)SMe}(CO) 2(?5-C5H5)] reveals the first example of a vinyl group bonded to a metal via both carbon atoms and therefore acting as a three-electron donor ligand. The structure consists of an approximately octahedrally co-ordinated tungsten atom bonded to an ?5-C5H5 ligand which occupies one face of the octahedron. Two carbonyl ligands occupy two octahedral sites while the third is occupied by the ?2-C(CF3)C(CF3)C(O)SMe ligand which adopts an orientation such that the vinylic C-C axis lies approximately parallel to one of the W-CO axes.

Original languageEnglish
Pages (from-to)2167-2176
Number of pages10
JournalJournal of the Chemical Society, Dalton Transactions
Issue number10
DOIs
Publication statusPublished - 1984

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