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Oxidative Addition of Water to Ir(I) Complexes Bearing a Pincer-Type Silyl Ligand.


ABSTRACT: Reaction of water with in situ generated [(PSiP-R)IrI] (PSiP-R = [{2-(R2P)C6H4}2MeSi]-; R = cyclohexyl, tBu or iPr) from [(PSiP-R)Ir(H)4] and tert-butylethylene (tbe) showed high ligand dependency. Oxidative addition of water cleanly proceeded in the reaction of [(PSiP-tBu)IrI] in THF at room temperature to selectively afford a 16-electron hydrido-hydroxo complex [(PSiP- t Bu)Ir(H)(OH)] almost quantitatively. In contrast, the reaction of cyclohexyl and iPr derivatives was unselective and formed various products containing Ir-H bonds. In the case of iPr-derivative, a small amount of 18-electron hydrido-hydroxo aqua complex [(PSiP-iPr)Ir(H)(OH)(H2O)] was isolated and structurally characterized by X-ray crystallography.

SUBMITTER: Fang H 

PROVIDER: S-EPMC9201899 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature

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Oxidative Addition of Water to Ir(I) Complexes Bearing a Pincer-Type Silyl Ligand.

Fang Hongyun H   Shimada Shigeru S  

ACS omega 20220601 23


Reaction of water with in situ generated [(PSiP-R)Ir<sup>I</sup>] (PSiP-R = [{2-(R<sub>2</sub>P)C<sub>6</sub>H<sub>4</sub>}<sub>2</sub>MeSi]<sup>-</sup>; R = cyclohexyl, <i>t</i>Bu or <i>i</i>Pr) from [(PSiP-R)Ir(H)<sub>4</sub>] and <i>tert</i>-butylethylene (tbe) showed high ligand dependency. Oxidative addition of water cleanly proceeded in the reaction of [(PSiP-<i>t</i>Bu)Ir<sup>I</sup>] in THF at room temperature to selectively afford a 16-electron hydrido-hydroxo complex [(PSiP- <sup><i>t<  ...[more]

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