Oxidative Addition of Water to Novel Ir(I) Complexes Stabilized by Dimethyl Sulfoxide Ligands
- 8 December 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 124 (2) , 188-189
- https://doi.org/10.1021/ja016625u
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(OCMe2)2]PF6 (5). These complexes add water at room temperature, giving rise to the oxidative addition products syn-[(DMSO)2HIr(μ-OH)2(μ-Cl)IrH(DMSO)2] [IrCl2(DMSO)2] (3) and anti-[(DMSO)2(DMSO)HIr(μ-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.Keywords
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