SYNTHESIS OF DIIRIDIUM COMPLEXES CONTAINING BRIDGING THIOLATE AND THIOETHER LIGANDS [(ETA(5)-C5ME5)IR(MU-SR)(MU-MESR)-IR(ETA(5)-C5ME5)][OSO2CF3] (R=PR-I, CYCLOHEXYL) AND THEIR REACTIVITIES TOWARD CO AND H-2

摘要

Treatment of [Cp*Ir(mu-SR)(2)IrCp*] (Cp*=eta(5)-C5Me5, R=Pr-i, Cy; Cy=cyclohexyl) with MeOTf (OTf=OSO2CF3) afforded the thiolate-and thioether-bridged diiridium complexes [Cp*Ir(mu-SR) (mu-MeSR)IrCp*][OTf](3). Upon heating a THF solution of 3a (R=Pr-i) under N-2, dissociation of the bridging MeSPri ligand took place and a coordinatively unsaturated complex [Cp*Ir(mu-SPri)IrCp*] [OTf] (4) was isolated in an analytically pure form, and characterized spectroscopically. When 3a was treated analogously under CO, a diiridium carbonyl complex [Cp*Ir(CO) (mu-SPri)IrCp*(CO)] [OTf] (5) was obtained in 53% yield together with 4 (39% yield). On the other hand, reactions of 3 with H-2 under similar conditions resulted in the formation of diiridium complexes bridged by two hydride and one thiolate ligands [Cp*Ir(mu-H)(2)(mu-SR)IrCp*] [OTf] (6) in high yields. The structure of 6 was determined by X-ray analysis using a single crystal of [Cp*Ir(mu-H)(2)(mu-SCy) IrCp*] [BPh4] derived from 6b (R=Cy). (C) 1997 Elsevier Science S.A. [References: 26]