Sogbein Oyebola O, Green Andrew E C, Schaffer Paul, Chankalal Raymond, Lee Edwin, Healy Brian D, Morel Pierre, Valliant John F
Department of Chemistry, McMaster University, Hamilton, Ontario L8S 4M1, Canada.
Inorg Chem. 2005 Dec 12;44(25):9574-84. doi: 10.1021/ic0511221.
A series of metallocarboranes of the types rac-[M(CO)3(eta(5)-7-R-7,8-C2B9H11)]-, rac-[M(CO)3(eta(5)-7-R-8-R'-7,8-C2B9H11)]-, and rac-[M(CO)3(eta(5)-7-R-7,9-C2B9H11)]- (M=Re) were prepared by reacting [NEt4]2[Re(CO)3Br3] or [Re(CO)3(OH2)3]Br with the corresponding carboranes in the presence of aqueous solutions of either alkali metal or tetraalkylammonium fluoride salts. Carborane derivatives that were investigated included those containing pyridine, amino, carboxylic acid, carbohydrate, and aryl substituents. During the course of the research, it was discovered that Re metallocarboranes can be prepared directly from the respective closo-clusters under similar reaction conditions used with nido-carboranes. Reaction yields ranged from modest to excellent depending on the carborane isomer and the nature of the cage substituent(s). A crystal structure of an amine-substituted Re metallocarborane was obtained where the complex crystallized in the orthorhombic space group P2(1)2(1)2(1) with a=8.982(2) A, b=11.563(3) A, c=16.811(4) A, alpha=beta=gamma=90 degrees, V=1746.1(7) A3, Z=4, and R1=0.0684.
通过使[NEt4]2[Re(CO)3Br3]或[Re(CO)3(OH2)3]Br与相应的碳硼烷在碱金属或四烷基氟化铵盐水溶液存在下反应，制备了一系列rac-[M(CO)3(η(5)-7-R-7,8-C2B9H11)]-、rac-[M(CO)3(η(5)-7-R-8-R'-7,8-C2B9H11)]-和rac-[M(CO)3(η(5)-7-R-7,9-C2B9H11)]-（M = Re）型金属碳硼烷。所研究的碳硼烷衍生物包括含有吡啶、氨基、羧酸、碳水化合物和芳基取代基的那些。在研究过程中，发现可以在与巢式碳硼烷相同的反应条件下直接从相应的闭式簇制备Re金属碳硼烷。根据碳硼烷异构体和笼状取代基的性质，反应产率从中等到优异不等。获得了一种胺取代的Re金属碳硼烷的晶体结构，该配合物在正交空间群P2(1)2(1)2(1)中结晶，a = 8.982(2) Å，b = 11.563(3) Å，c = 16.811(4) Å，α = β = γ = 90°，V = 1746.1(7) Å3，Z = 4，R1 = 0.0684。
