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

被引:13
作者
Nishio, M [1 ]
Mizobe, Y [1 ]
Matsuzaka, H [1 ]
Hidai, M [1 ]
机构
[1] UNIV TOKYO,GRAD SCH ENGN,DEPT CHEM & BIOTECHNOL,BUNKYO KU,TOKYO 113,JAPAN
关键词
iridium complexes; thiolate complexes; thioether complexes; hydride complexes; dinuclear complexes; crystal structures;
D O I
10.1016/S0020-1693(97)05709-5
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
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.
引用
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页码:59 / 63
页数:5
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