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Dynamic Permutational Isomerism in a closo-Cluster

机译:Closo-Cluster中的动态排列异构

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Permutational isomers of trigonal bipyramidal [W2RhIr2(CO)(9)((5)-C5H5)(2)((5)-C5HMe4)] result from competitive capping of either a W2Ir or a WIr2 face of the tetrahedral cluster [W2Ir2(CO)(10)((5)-C5H5)(2)] from its reaction with [Rh(CO)(2)((5)-C5HMe4)]. The permutational isomers slowly interconvert in solution by a cluster metal vertex exchange that is proposed to proceed by Rh-Ir and Rh-W bond cleavage and reformation, and via the intermediacy of an edge-bridged tetrahedral transition state. The permutational isomers display differing chemical and physical properties: replacement of CO by PPh3 occurs at one permutational isomer only, while the isomers display distinct optical power limiting behavior.
机译:四面体簇[W2RhIr2(CO)(9)((5)-C5H5)(2)((5)-C5HMe4)的排列异构体是由四面体簇[W2Ir2(W2Ir2( CO)(10)((5)-C5H5)(2)]与[Rh(CO)(2)((5)-C5HMe4)]的反应。排列异构体在溶液中通过簇金属顶点交换在溶液中缓慢互变,该交换提议通过Rh-Ir和Rh-W键的裂解和重整,并通过边缘桥联的四面体过渡态进行。排列异构体显示出不同的化学和物理性质:仅在一个排列异构体上,PPh3取代CO发生,而异构体显示出不同的光功率限制行为。

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