铑(Ⅰ)催化有机汞化合物偶联反应机理的研究

Studies on the Mechanism of Dimerization of Organomercuric Compounds by Rhodium(Ⅰ)

研究了β-氯化萘汞在［CIRh（CO）2］2催化下于六甲基磷酰胺溶液中的偶联反应动力学，证明其反应为二级，求得了偶联反应动力学常数．α-氯化萘汞和α-溴汞代苯乙酸乙酯在相同的反应条件下不发生偶联反应；在α一溴汞代苯乙酸乙酯的偶联反应条件下分离和鉴定了有机铑（I）中间体，根据所提出的反应机理，对上述现象进行了讨论．

The kinetics of dimerlzation of β-naphthylmercuric chloride in the presence of[CIRh (CO)2]2 has been studied in hexamethylphosphoramide. The dimerization has beenfound to be second order and the kinetic parameters of the dimerization have been reported.Both α-naphthylmercuric chloride and α-bromomercuriphenylacetate have not beendimerizated under the same reaction conditions, which has been explained on the basis of the proposedmechanism. The organic rhodium (I) intermediate formed in the α-bromonercuriphenylacetate case was isolated and identified.