两种乙酰丙酮·羰基铑化合物的合成与晶体结构表征  

Synthesis and Crystal Structure Characterization of Two Rhodium Carbonyl Compounds

作　　者：余娟[1] 叶青松[1] 沈善问[1] 左川[1] 刘桂华[1] 刘伟平[1] 

机构地区：[1]昆明贵金属研究所稀贵金属综合利用新技术国家重点实验室,昆明650106

出　　处：《贵金属》2016年第2期8-12,25,共6页Precious Metals

基　　金：国家科技支撑计划(2012BAE06B08);云南省科技创新(2015AA006);稀贵金属国家重点实验室开放课题(2014020605)

摘　　要：在N,N-二甲基甲酰胺介质中,将水合三氯化铑与乙酰丙酮加热回流,一步合成了乙酰丙酮·二羰基铑([Rh(CO)2(acac)]2),产率为93%;以正丁烷为介质,[Rh(CO)2(acac)]2与三苯基磷(PPh3)定量反应,得到乙酰丙酮·三苯基膦·羰基铑(Rh(acac)(PPh3)(CO)),产率为99%。用气相扩散法和溶剂缓慢挥发法分别培养出[Rh(CO)2(acac)]2和Rh(acac)(PPh3)(CO)单晶,元素分析的结果表明产物为目标化合物。用X射线单晶衍射仪对其结构进行了表征,获得了晶体结构参数,结果表明2种化合物均为三斜晶系、P-1空间群,[Rh(CO)2(acac)]2为二聚体化合物,Rh(acac)(PPh3)(CO)为单核配合物。Rh(CO)2(acac)]2 was synthesized in one-step process from RhCl3·3H2O in DMF by adding acac as the anion ligand. The yield was 93%. A quantitative reaction between [Rh(CO)2(acac)]2 and PPh3 in n-butane gave rise to the formation of Rh(acac)(PPh3)(CO) with a yield of 99%. Single crystals of two complexes were prepared, respectively, via a gaseous diffusion method and a solvent evaporation technique, and were subjected to X-ray diffraction analysis. The results show both complexes are in the triclinic system with a space group of P-1. [Rh(CO)2(acac)]2 displays a dimmeric structure with Rh-Rh bond being 3.417 ?, whereas Rh(acac)(PPh3)(CO) has a normal mononuclear structure.

关 键 词：有机化学 乙酰丙酮·二羰基铑 乙酰丙酮·三苯基膦·羰基铑 合成 晶体结构 

分 类 号：O627.8[理学—有机化学] TQ426.94[理学—化学]