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Issue 3, 1985
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Hexakis(trimethylphosphine)molybdenum chemistry: dinitrogen, ethylene, butadiene, η-cyclopentadienyl, and related derivatives

Abstract

Co-condensation of molybdenum atoms with trimethylphosphine gives octahedral [ Mo(PMe3)6](1) whose crystal structure has been determined. Treatment of (1) with dinitrogen, ethylene, carbon monoxide, iodine, or butadiene gives [Mo(N2)(PMe3)5], trans-[Mo(η-C2H4)2(PMe3)4]fac-[Mo(CO)3(PMe3)3], trans-[MoI2(PMe3)4], and cis-[Mo(η-C4H6)2(PMe3)2] respectively. Protonation of cis-[Mo(η-C4H6)2(PMe3)2] with tetrafluoroboric acid forms the compound cis-[[graphic omitted]CH2CHCHCH2)(η-C4H6)(PMe3)2]BF4. The presence of the Mo–H–C bond is shown by low-temperature n.m.r. spectra, and variable-temperature n.m.r. shows that the agostic hydrogen can scramble between the four terminal carbons of the two C4 ligands. The rate constants and activation parameters for the hydrogen-scrambling process have been determined and a mechanism is proposed. Reaction of cis-[Mo(η-C4H6)2(PMe3)2] with trifluoroacetic acid gives [Mo(η-MeC3H4)(η-C4H6)(PMe3)2(O2CCF3)]. Treatment of [Mo(PMe3)6] with cyclopentadiene forms [MoH(η-C5H5)(PMe3)3] which reacts with aqueous tetrafluoroboric acid giving [MoH2(η-C5H5)(PMe3)3]BF4 and [Mo(η-C5H5)(PMe3)2O]BF4. Reaction of [MoH(η-C5H5)(PMe3)3] with methyl iodide gives [MoH(η-C5H5)(PMe3)2I2].

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Article information


J. Chem. Soc., Dalton Trans., 1985, 423-433
Article type
Paper

Hexakis(trimethylphosphine)molybdenum chemistry: dinitrogen, ethylene, butadiene, η-cyclopentadienyl, and related derivatives

M. Brookhart, K. Cox, F. G. N. Cloke, J. C. Green, M. L. H. Green, P. M. Hare, J. Bashkin, A. E. Derome and P. D. Grebenik, J. Chem. Soc., Dalton Trans., 1985, 423
DOI: 10.1039/DT9850000423

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