Substitution and isomerisation reactions at platinum(II) involving halide, tertiary phosphine, carbonyl, and lsonitrile ligands
作者:Ronald J. Cross、Ian G. Phillips
DOI:10.1039/dt9820002261
日期:——
Carbon monoxide catalyses trans to cis isomerisations of [PtCl2L2](L = tertiaryphosphine) in chloroform solution. The process involves formation of five-co-ordinate intermediates from which halide or tertiaryphosphine can be eliminated, giving trans-[PtCl(CO)L2]+ or cis-[ PtCl2(CO)L] respectively. Structure changes appear to be by pseudo-rotations rather than by consecutive displacements. A number
一氧化碳催化作用反式到顺式的异构化[氯铂酸2大号2的氯仿溶液](L =叔膦)。该方法涉及形成五个坐标的中间体,可以从中除去卤化物或叔膦,分别得到反式-[PtCl(CO)L 2 ] +或顺式-[PtCl 2(CO)L]。结构变化似乎是通过伪旋转而不是连续的位移。许多异腈配合物会经历类似的反应。卤化物桥接阳离子[Pt 2(µ-Cl)2 L 4 ] 2+由Ag +从顺式-[PtCl 2 L 2 ]的卤化物萃取中形成的合物在环境温度下进入与后者配合物的快速(nmr时间标度)交换过程。用溶剂氯仿从顺式-[PtCl 2 L 2 ]中消除卤化物似乎启动了该过程。该反式异构体不参与交流。
Preparation of the complexes trans-[PtX2(CO)L] and their isomerisation to cis isomers
作者:Gordon K. Anderson、Ronald J. Cross
DOI:10.1039/dt9800001988
日期:——
halide; L is tertiary phosphine or arsine) by carbon monoxide gives solutions of the trans isomers of [PtX2(CO)L], some of which can be isolated. These compounds readily lose CO and isomerise to cis derivatives. The trans to cisisomerisations are catalysed by free CO, phosphines, or halide ions, and the latter nucleophile operates even in the solid phase. Free CO exchanges with co-ordinated CO more rapidly