Synthesis and diphosphine ligand fluxionality in Os3(CO)10(bmi): Kinetic evidence for nondissociative diphosphine isomerization and X-ray crystal structure of 1,1-Os3(CO)10(bmi)
作者:William H. Watson、Bhaskar Poola、Michael G. Richmond
DOI:10.1016/j.jorganchem.2006.07.040
日期:2006.11
The triosmium cluster 1,2-Os3(CO)10(MeCN)2 reacts rapidly with the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at room temperature to give bmi-bridged cluster 1,2-Os3(CO)10(bmi) (2b) as the major product, along with the chelating isomer 1,1-Os3(CO)10(bmi) (2c) and the hydride-bridged cluster HOs3(CO)9[μ-(PPh2)CCPPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) as minor by-products. All
os簇1,2-Os 3(CO)10(MeCN)2在室温下与二膦配体2,3-双(二苯基膦基)-N-对甲苯基马来酰亚胺(bmi)快速反应,得到bmi桥连簇1 ,2-Os 3(CO)10(bmi)(2b)作为主要产物,以及螯合异构体1,1-Os 3(CO)10(bmi)(2c)和氢化物桥接的簇HOs 3( CO)9 [μ-(PPh 2)CC PPh(C 6 H 4)} C(O)N(tolyl- p)C(O)](3)作为次要产品。所有三种簇化合物均已分离,并在溶液中通过IR和NMR光谱法(1 H和31 P)进行了充分表征,在2c的情况下通过X射线晶体学进行了表征。团簇2b是不稳定的,并且在温和加热下容易以定量产率异构化为2c。用于转化的动力学图2b → 2C已经测量的温度范围内的甲苯溶液318-348的K,并且基于观察到的激活参数nondissociative异构化方法,其经由瞬态μ前进2