title: Oxidative addition of water to novel Ir(I) complexes stabilized by dimethyl sulfoxide ligands.
abstract: The oxidative addition of water to novel Ir(I) DMSO complexes is described. IrCl(DMSO)3 (1) is synthesized in 90% yield when treating a toluene slurry of [Ir2Cl2(COE)4] (COE = cyclooctene) with excess DMSO. Its dimer, [Ir2Cl2(DMSO)4] (2) is obtained in 95% yield starting from 1. The cationic complex [Ir(DMSO)4]PF6 (6) is prepared in situ from [Ir(COE)2(O=CMe2)2]PF6 (5). These complexes add water at room temperature, giving rise to the oxidative addition products syn-[(DMSO)2HIr(mu-OH)2(mu-Cl)IrH(DMSO)2] [IrCl2(DMSO)2] (3) and anti-[(DMSO)2(DMSO)HIr(mu-OH)2IrH(DMSO)2(DMSO)](PF6)2 (7), respectively. Reductive elimination in pyridine leads to quantitative isolation of mixed Ir(I) DMSO-pyridine complexes IrCl(py)(DMSO)2 (4) and [Ir(py)2(DMSO)2]PF6 (8), respectively. Compounds 1, 3, and 7 have been characterized by X-ray crystallography. 3 and 7 show dimeric structures with the hydroxo ligands bridging the iridium atoms and in 7 both O- and S-bonded DMSO ligands are present.
authors.affiliation: Departments of Organic Chemistry and Chemical Services, The Weizmann Institute of Science, Rehovot 76100, Israel.
authors.forename: Reto
authors.initials: R
authors.lastname: Dorta
authors.forename: Haim
authors.initials: H
authors.lastname: Rozenberg
authors.forename: Linda J W
authors.initials: LJ
authors.lastname: Shimon
authors.forename: David
authors.initials: D
authors.lastname: Milstein