The complexes cis- and trans-[OsX2(dcpe)2][X = Cl or Br; dcpe = 1,2-bis(dicyclohexylphosphino)-ethane] have been prepared, and their physical and chemical properties investigated. The cis isomers were found to dissociate quickly in polar solvents to give [OsX(dcpe)2]+, which have been isolated in the solid state as the tetraphenylborate salts. On the basis of 31P n.m.r. and u.v.–visible spectra, the
配合物的顺式-和反式- [OSX 2(D
CPE)2 ] [X = Cl或Br; 制备了d
CPE = 1,2-双(
二环己基膦基)-
乙烷,并对其物理
化学性质进行了研究。所述顺式被发现的异构体,以在极性溶剂中离解迅速,得到[OSX(D
CPE)2 ] +,其已在固体状态下被分离为四苯基
硼酸盐。根据31 P nmr和uv可见光谱,为d 6阳离子分配了一个三角双锥体结构,卤化物处于赤道位置。不饱和配合物[OSX(d
CPE)2 ] +在
二氯甲烷溶液中容易地和立体选择性地添加卤化物或中性
配体L(CO,MeCN或PhCN)以形成相应的顺式衍
生物。所述顺式- [OSX(L)(D
CPE)2 ] +阳离子可以被热转化成反式异构体。发现以前曾与X –和L进行反式加成的类似[RuX(d
CPE)2 ] +物种形成顺式-[RuX 2(d
CPE)2 ]和顺式-[RuX(L)(d
CPE)2 ] +在–60°C的
二氯甲烷或
丙酮