Solid state isomerisation reactions of some ruthenium complexes
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- 作者：Nareetsile ; Florence M. ; Horwood ; Owen P.M. ; Billing ; David G. ; Levendis ; Demetrius C. ; Coville ; Neil J.
- 关键词：Ruthenium ; Solid state ; Isomerisation ; DSC ; Isonitrile
- 刊名：Journal of Organometallic Chemistry
- 出版年：2003
- 出版时间：October 1, 2003
- 年：2003
- 卷：682
- 期：1-2
- 页码：2-7
- 全文大小：278 K
文摘
The isomerisation of ttt-RuCl2(RNC)2(PPh3)2 (R=2,6-xylyl, tBu, iPr, benzyl, 2-OMe-4-Clphenyl) to cct-RuCl2(RNC)2(PPh3)2 has been carried out in the solid state. The reaction is first order and kinetic measurements have yielded activation energies of 210 kJ mol−1 (R=tBu) and 221 kJ mol−1 (R=benzyl) for reactions performed between 160 and 180°C. XRD analysis of the solid state reaction of ttt-RuCl2(tBuNC)2(PPh3)2 has revealed that the cct-isomer produced is a polymorph of that produced by recrystallisation of the pure cct-RuCl2(tBuNC)2(PPh3)2 isomer. A possible mechanism for the isomerisation reaction involving rotation of the two small groups (Cl, RNC) is proposed.