Department of Chemistry, University of Warwick, Coventry, UK CV4 7AL.
Chem Commun (Camb). 2012 Jun 11;48(46):5775-7. doi: 10.1039/c2cc31572f. Epub 2012 May 2.
Oxidation of a doubly cyclometallated platinum(II) complex results in two isomeric platinum(IV) complexes. Whereas the trans isomer is robust, being manipulable in air at room temperature, the cis isomer decomposes at -20 °C and above. Reductive coupling of an alkyl chloride at the cis isomer gives a new species which can be reoxidised. The independence of this coupling on additional halide rules out the reverse of an S(N)2 reaction, leaving a concerted process as the only sensible reaction pathway.
双环金属化铂(II)配合物的氧化导致两个顺式和反式异构体铂(IV)配合物的生成。反式异构体是稳定的，可以在室温下在空气中操作，而顺式异构体在-20°C 以上会分解。顺式异构体的卤代烷烃的还原偶联生成一种新的物种，可以被再次氧化。这种偶联与额外的卤化物无关，排除了 S(N)2 反应的逆反应，使协同反应成为唯一合理的反应途径。
