镓（C5Me4Ph）的配位化学：新型钯的同配体d10簇合物

Coordination chemistry of Ga(C5Me4Ph): novel homoleptic d10 cluster complexes of palladium.

作者信息

Buchin Beatrice, Gemel Christian, Cadenbach Thomas, Fischer Roland A

机构信息

Anorganische Chemie II, Organometallics & Materials, Bochum, Germany.

出版信息

Inorg Chem. 2006 Feb 20;45(4):1789-94. doi: 10.1021/ic051658m.

DOI:10.1021/ic051658m

PMID:16471995

Abstract

The synthesis and characterization of the novel sterically encumbered Ga(I) ligand GaCp(Ph) (1b) (Cp(Ph) = C5Me4Ph) is presented. GaCp(Ph) reacts with the Pd(0) source Pd2(dvds)3 (dvds = tetramethyldivinyldisiloxane) to give the trinuclear cluster [Pd3(GaCp(Ph))(mu2-GaCp(Ph))(mu3-GaCp(Ph))2(dvds)] (2a). 2a is the first example of a Ga(I)-containing cluster with a potentially labile olefinic ligand. It was found that 2a is an intermediate in the formation of the dinuclear cluster [Pd2(GaCp(Ph))2(mu2-GaCp(Ph))3] (2b), which is formed on reaction of 2a with GaCp(Ph). Both clusters were found to be labile toward GaCp, AlCp, or phosphines, giving substitution products in all cases.

摘要

本文介绍了新型空间位阻镓（I）配体GaCp(Ph)（1b）（Cp(Ph) = C5Me4Ph）的合成与表征。GaCp(Ph)与钯（0）源Pd2(dvds)3（dvds = 四甲基二乙烯基二硅氧烷）反应生成三核簇合物[Pd3(GaCp(Ph))(μ2-GaCp(Ph))(μ3-GaCp(Ph))2(dvds)]（2a）。2a是含镓（I）簇合物中首个带有潜在不稳定烯烃配体的例子。研究发现2a是双核簇合物[Pd2(GaCp(Ph))2(μ2-GaCp(Ph))3]（2b）形成过程中的中间体，2b是2a与GaCp(Ph)反应生成的。结果表明，这两种簇合物对GaCp、AlCp或膦都不稳定，在所有情况下都会生成取代产物。