Preparation and Characterization of Dinuclear Metal Complexes, [(PPh3)2(CO)M(￥ì-E)M(CO)(PPh3)2](SO3CF3)2 (M = Rh, Ir; E = 1,4-Dicyanobenzene and 1,4-Dicyano-2-butene)

摘要

Hydrocarbon solution of (PPh3)2(CO)MOSO2CF3 (M= Rh, Ir) reacts rapidly with 1,4-dicyanobenzene or 1,4-dicyano-2-butene to yield dinuclear metal complexes [(PPh3)2(CO)M(レ -dicyanobenzene)M(CO)(PPh3)2](SO3CF3)2 (グ: M = Rh; ケ: M = Ir) or [(PPh3)2(CO)M(レ -dicyano-2-benzene)M(CO)(PPh3)2](SO3CF3)2 (ゲ: M = Rh; コ: M = Ir), respectively. Compounds グ, ケ, ゲ, and コ were characterized by 1H-NMR, 31P-NMR, and infrared spectrum. Dichloromethane solution of ケ and コ reacts with H2 and I2 to yield oxidative addition complexes [(PPh3)2(CO)IrX2(レ-E)X2Ir(CO)(PPh3)2] (SO3CF3)2 (ゴ; E = 1,4-dicyanobenzene, X2 = H2; サ : E = 1,4-dicyano-2-butene, X2 = H2; ザ; E = 1,4-dicyanobenzene, X2 = I2). All metal complexes are bridged by the cyanide groups. Compounds ゴ, サ, and ザ are characterized by conventional methods.