Control of intramolecular acetate–allenylidene coupling by spectator co-ligand π-acidity

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Karsten J. Harlow, Anthony F. Hill and Thomas Welton


Abstract

The reactions of [RuHX(PPh3)3] (X = Cl, 02CMe) and [MHCl(C0)(PPh3)3] (M = Ru, 0s) with 1,1-diphenylprop-2-yn-1-ol provide convenient access to alkynyl, alkenyl, propenylidene, and acetoxyallenyl complexes of divalent ruthenium and osmium, including [RuCl2(=CHCH=CPh2)(PPh3)2] and the complexes [Ru(C[triple bond, length half m-dash]CCPh20H)-(02CMe)(CA)2(PPh3)2] (A = NCMe3, 0), protonation (HPF6) of which provides [Ru(02CMe)(=C=C=CPh2)-(CNCMe3)2(PPh3)2]PF6 or the metallacycle [Ru{κ2C, 0-C(=C=CPh2)02CMe}(C0)2(PPh3)2]PF6, respectively.


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