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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts
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The influence of steric bulk on the geometry of triarylphosphite-based palladacycles and their tricyclohexylphosphine adducts

机译:空间体积对基于三芳基亚磷酸酯的palladacycles及其三环己基膦加合物的几何形状的影响

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摘要

A range of complexes of the formula [PdCl2{P(OAr)(3)}(2)] have been synthesized in order to determine the effect of steric bulk on stereochemistry, one example [PdCl2{P(OC6H4-2-Bu-t)(3)}(2)] has been structurally characterized. Three palladacyclic complexes [{Pd(mu-Cl)-(kappa(2)-P, C-P(OC6H3R)(OC6H4R)(2))}(2)] have been synthesized (R = H, 2-Pr-t, 2-Bu-t) and two have been characterized by crystallography (R = H and Bu-t). The latter adopts the expected trans geometry while the former is cis. In this case, the driving force for the cis geometry seems to be intermolecular interactions in the crystal structure which are disrupted on substitution. We also report an unusual solvolysis reaction. (c) 2005 Elsevier Ltd. All rights reserved.
机译:为了确定空间体积对立体化学的影响,已经合成了一系列式[PdCl2 {P(OAr)(3)}(2)]的配合物,一个例子是[PdCl2 {P(OC6H4-2-Bu- t)(3)}(2)]已在结构上得到了表征。合成了3个四环化合物[{Pd(mu-Cl)-(kappa(2)-P,CP(OC6H3R)(OC6H4R)(2))}(2)(R = H,2-Pr-t, 2-Bu-t)和两个已经通过晶体学表征(R = H和Bu-t)。后者采用预期的反式几何形状,而前者为顺式。在这种情况下,顺式几何结构的驱动力似乎是晶体结构中的分子间相互作用,该相互作用在取代时会中断。我们还报告了异常的溶剂分解反应。 (c)2005 Elsevier Ltd.保留所有权利。

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