F.G.A. Stone, Robert West (Eds.)'s Advances in Organometallic Chemistry, Vol. 29 PDF

By F.G.A. Stone, Robert West (Eds.)

ISBN-10: 0120311291

ISBN-13: 9780120311293

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Four-Electron Alkyne Ligands 23 00 (C0)3(PPh3)Br to an anionic acyl complex can be realized with methyllithium addition, effectively initiating the classic Fischer carbene preparation. Addition of oxalyl bromide, still at -78"C, would be expected to generate a biscarbyne precursor complex as shown in Eq. (48). Addition of excess triphenylphosphine and warming to room temperature produce a deep blue solution which yields W(CO)(P~CECM~)(PP~~)~B~~, previously characterized by Davidson and Vasapollo (48).

5 ppm) indicative of fourelectron donation from the alkyne (60). Alkyne carbons in W(MA)(PhC=CH)(S,CNEt,), appear near 223 ppm in the 13C-NMR spectrum, somewhat below the 206 ppm chemical shift of the alkyne in the carbonyl The parent acetylene ligand, analog, W(CO)(PhC=CH)(S,CNEt,),. HC=CH, produces only a singlet in the 'H spectrum of both the DCNE and MA tungsten derivatives even at low temperature (-99°C). The two ends of the alkyne are not equivalent by symmetry, and facile alkyne rotation is suggested by these results.

Qualitative molecular orbital presentations based on octahedral models have been reinforced by calculations on various d monomers, but the essence of alkyne binding through TI/* acceptance and 7rl donation as reflected in orientational preferences has remained intact. A theoretical comparison of three diverse model compounds designed to mimic the bonding in structurally characterized diphenylacetylene adducts has probed T~ donation (141). Identifying free PhCECPh as 1 allows use of the mnemonic labels 2, 3, and 4 for the alkyne adducts Cp2Mo(PhCSCPh), Mo(SR),(CNR),(PhC=CPh), and Mo(TTP)(PhC=CPh), respectively.

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Advances in Organometallic Chemistry, Vol. 29 by F.G.A. Stone, Robert West (Eds.)

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