Factors governing the equilibrium between metal-alkyl, alkylidene and alkylidyne:: MCX2R, X-M=CXR and X2MCR

被引：64

作者：

Caulton, KG ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2001年 / 617卷 / 01期

关键词：

carbene complexes; alkylidene; alkylidyne;

D O I：

10.1016/S0022-328X(00)00706-3

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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.

引用

页码：56 / 64

页数：9

共 14 条

[1]

Coalter JN, 2000, NEW J CHEM, V24, P835

[2] Cleavage of H-C(sp2) and C(sp2)-X bonds (X = alkyl, aryl, OR, NR2):: Facile decarbonylation, isonitrile abstraction, or dehydrogenation of aldehydes, esters, amides, amines, and imines by [RuHCl(PiPr3)2]2 [J].