Issue 12, 1987
From the journal:

Journal of the Chemical Society, Dalton Transactions

The chemistry of cycloheptatrienyl complexes of molybdenum and tungsten: the synthesis and reactions of some vinylidene and alkynyl derivatives

Jeanette S. Adams,   Caroline Bitcon,   Jack R. Brown,   David Collison,   Michael Cunningham  and  Mark W. Whiteley  

Abstract

Reaction of the terminal alkyne HC[triple bond, length half m-dash]CPh with [Mo(sol)(dppe)(η-C7H7)][PF6][(2a), sol = NCMe; (2b), sol = acetone; dppe = Ph2PCH2CH2PPh2] in refluxing acetone yields the phenylvinylidene complex [Mo(C[double bond, length half m-dash]CHPh)(dppe)(η-C7H7)][PF6](3) which is readily deprotonated to give the alkynyl complex [Mo(C[triple bond, length half m-dash]CPh)(dppe)(η-C7H7)](4). A similar reaction sequence-starting from HC[triple bond, length half m-dash]CBut and (2b) yields [Mo(C[triple bond, length half m-dash]CBut)(dppe)(η-C7H7)](6). Protonation of (4) with H[BF4]·Et2O reforms [Mo(C[double bond, length half m-dash]CHPh)(dppe)(η-C7H7)]+. Electrochemical studies show that (4) and (6) undergo a reversible one-electron oxidation at a glassy carbon electrode in CH2Cl2 and chemical oxidation with [Fe(η-C5H5)2][BF4] yields the radical cations [Mo(C[triple bond, length half m-dash]CR)(dppe)(η-C7H7)][BF4][(5), R = Ph; (7), R = But] which have been studied by e.s.r. spectroscopy. Reaction of LiC[triple bond, length half m-dash]CPh with [MX(CO)2(η-C7H7)](M = Mo or W; X = I or Cl) affords the parent dicarbonylalkynyl complexes [M(C[triple bond, length half m-dash]CPh)(CO)2(η-C7H7)][(8), M = Mo; (9), M = W].

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Article information

DOI
https://doi.org/10.1039/DT9870003049
Article type
Paper

J. Chem. Soc., Dalton Trans., 1987, 3049-3053

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The chemistry of cycloheptatrienyl complexes of molybdenum and tungsten: the synthesis and reactions of some vinylidene and alkynyl derivatives

J. S. Adams, C. Bitcon, J. R. Brown, D. Collison, M. Cunningham and M. W. Whiteley, J. Chem. Soc., Dalton Trans., 1987, 3049 DOI: 10.1039/DT9870003049

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