Deprotonation and Oxidation of the W⋮CCH2−W Bridge To Form a C2-Biscarbyne W⋮C−C⋮W Bridge
Journal of the American Chemical Society1998Vol. 120(35), pp. 9028–9033
Citations Over TimeTop 15% of 1998 papers
Abstract
Reaction of the anionic vinylidene complex K[Tp‘(CO)2MCCH2] (M = Mo, W; Tp‘ = hydridotris(3,5-dimethylpyrazolyl)borate) with Tp(CO)(PhC⋮CPh)W−I (Tp = hydridotris(pyrazolyl)borate) yields Tp‘(CO)2MCCH2−W(CO)(PhC⋮CPh)Tp (M = Mo, 4; W, 5) and potassium iodide. Removal of a methylene proton from the (⋮CCH2−) bridge with KOBut forms a monoanion containing a putative carbene moiety. Oxidation of the anion with iodine leads to net hydride removal and yields the unusual C2-bridged dimers Tp‘(CO)2M⋮CC⋮W(CO)(PhC⋮CPh)Tp (M = Mo, 7; W, 8). Conversion of the tungsten−carbon single bond in the precursor complex to a triple bond in the product is accompanied by a significant reduction in donation to the metal from the alkyne π⊥ orbital.
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