Oxidative addition of water to novel Ir(I) complexes stabilized by dimethyl sulfoxide ligands

Reto Dorta, Haim Rozenberg, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

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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(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.

Original languageEnglish
Pages (from-to)188-189
Number of pages2
JournalJournal of the American Chemical Society
Volume124
Issue number2
DOIs
Publication statusPublished - Jan 16 2002

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Dimethyl sulfoxide
Dimethyl Sulfoxide
Pyridine
Ligands
Water
X ray crystallography
Iridium
Dimers
Toluene
Atoms
Temperature
X Ray Crystallography

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Oxidative addition of water to novel Ir(I) complexes stabilized by dimethyl sulfoxide ligands. / Dorta, Reto; Rozenberg, Haim; Shimon, Linda J W; Milstein, David.

In: Journal of the American Chemical Society, Vol. 124, No. 2, 16.01.2002, p. 188-189.

Research output: Contribution to journalArticle

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N2 - 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(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.

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