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Syntheses and reactivity of neutral iron and ruthenium vinylidene complexes

Stephen J. Walters, Harry Adams, Neil A. Bailey, Peter R.G.A. Salmon, Claire Sumner, and Mark J. Winter

Department of Chemistry, The University, Sheffield S3 7HF, UK.


The anions [M(SnPh3)(CO)(COCH2R)(h-C5H5)]- (M = Fe, Ru; R = H, Me, and Ph) react with MeCOCl to give acyl(oxy) carbenes M(SnPh3)(CO){=C(OCOMe)CH2R}(h-C5H5). These eliminate MeCO2H resulting in the neutral iron and ruthenium half-sandwich vinylidene complexes M(SnPh3)(CO)(=C=CHR)(h-C5H5). Deprotonation of these with LiBun affords reactive anionic h1-alkynyl complexes [M(SnPh3)(CO)(CCR1)(h-C5H5)]- which in turn react with electrophiles to afford new neutral vinylidene complexes M(SnPh3)(CO)(=C=CR1R2)(h-C5H5).


We present here syntheses and a few preliminary reactions of some neutral half-sandwich vinylidene complexes of iron and ruthenium. The results are reinforced by X-ray crystallographic data. These compounds are unusual since most vinylidene complexes are cationic and our neutral complexes therefore offer interesting synthetic possibilities.



© 1997 Mark Winter
Department of Chemistry at the University of Sheffield, Sheffield S3 7HF, England.