the cis form. When L = PMe2Ph, the ‘trans isomer’ formed is not trans-[OsCl2(PMe2Ph)4] and should be formulated as trans-[OsCl2(PMe2Ph)3(P′Me2Ph)] with a unique weakly bound phosphine. In non-co-ordinating media, concentrated solutions of [OsCl2(PMe2Ph)3] undergo further reactions to form doubly and triply bridged binuclear species such as [Os2Clq(PMe2Ph)6] and [Os2Cl3(PMe2Ph)6]+. This series of electroinitiated
[OsCl 3(PMe 2 Ph)3 ]的电还原后,可以稳定并表征反应性单阴离子[OsCl 3(PMe 2 Ph)3 ] -。该单阴离子可轻松释放
氯离子,得到可检测的五坐标中间体,该中间体可进一步与供体溶剂或可用的
配体反应生成[OsCl 2(PMe 2 Ph)3 L](L = MeCN,二甲基甲酰胺,
二甲基亚砜,PhCN, CO,N 2或C 2 H 4),最初是反式异构体。后者可以转换为顺式形式。当L = PMe 2 Ph时,形成的“反式异构体”不是反式-[OsCl 2(PMe 2 Ph)4 ],应配制成反式-[OsCl 2(PMe 2 Ph)3(P'Me 2 Ph) ]具有独特的弱结合膦。在非配位介质中,[OsCl 2(PMe 2 Ph)3 ]的浓缩溶液会进一步反应,形成双和三重桥接的双核物种,例如[Os 2 Clq(PMe 2 Ph)6 ]和[Os 2 Cl 3(PMe 2 Ph)6 ]