Electrophilic addition vs electron transfer for the interaction of Ag{sup +} with molybdenum(II) hydrides. 2. Reaction with CpMoH(CO){sub 2}(PMe{sub 3})
- Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry
- Univ. de Bourgogne, Dijon (France)
The interaction of CpMoH(CO){sub 2}(PMe{sub 3}), 1, with AgBF{sub 4} in acetonitrile establishes an equilibrium (K = 9 {+-} 1) with the hydride-bridged adduct [Cp(CO){sub 2}(PMe{sub 3})Mo({mu}-H)Ag(MeCN){sub x}]BF{sub 4}, 4, which is in a fast chemical exchange on the NMR time scale with compound 1. The interaction of 1 and AgBF{sub 4} in THF leads to the formation of the trinuclear complex {l_brace}[CpMoH-(CO){sub 2}(PMe{sub 3})]{sub 2}Ag{r_brace}BF{sub 4}, 5, as an insoluble white solid in 73% yield when the Mo/Ag ratio is 2:1. The nature of the precipitate does not depend on the relative stoichiometry of the two reagents. When redissolved in acetonitrile, compound 5 dissociates, generating a mixture of 1 and 4. Compound 4 slowly evolves to the solvent adduct, [CpMo(CO){sub 2}(PMe{sub 3})(MeCN)]BF{sub 4}, 3, with elimination of hydrogen gas and metallic silver. The decomposition of 4 could be interpreted as either an inner-sphere electron transfer or a substitution of unstable AgH.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- OSTI ID:
- 315990
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 26 Vol. 17; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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