期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 617, 期 1, 页码 56-64出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/S0022-328X(00)00706-3
关键词
carbene complexes; alkylidene; alkylidyne
The reactions of vinyl ethers, H2C=CH(OR), with RuHClL2 (L = (PPr3)-Pr-i) furnish the carbene complexes RuHCl[C(CH3)(OR)]L-2 by H migration. Os(H)(3)ClL2 serves as a surrogate for unknown OsHClL2, to give the analogous carbene, but this transforms further for R=Ph to give the carbyne OsHCl(OPh)(CCH3)L-2. DFT calculations furnish insight into the relative thermodynamic stability of the various isomeric species, and are consistent with the major influence of pi -donation by OR, as well as the preference of Os (versus Ru) for saturation and higher oxidation state. Comparison of the reactivity of H2C=CHD0 (D-0 = pi -donor) towards MHClL2 versus Cp2ZrHCl shows the dominant influence of metal pi -donor power. Ruthenium and osmium complexes containing an MCF3 subunit show remarkably facile isomerization to FM=CF2 carbenes. (C) 2001 Published by Elsevier Science B.V.
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