Breaking C-O Bonds with Uranium: Uranyl Complexes as Selective Catalysts in the Hydrosilylation of Aldehydes - Archive ouverte HAL Access content directly
Journal Articles ACS Catalysis Year : 2019

Breaking C-O Bonds with Uranium: Uranyl Complexes as Selective Catalysts in the Hydrosilylation of Aldehydes

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1

Abstract

We report herein the possibility to perform the hydrosilylation of carbonyls, using actinide complexes as catalysts. While complexes of the uranyl ion [UO2]2+ have been poorly considered in catalysis, we show the potentialities of the Lewis acid [UO2(OTf)2] (1) in the catalytic hydrosilylation of a series of aldehydes. [UO2(OTf)2] proved a very active catalyst affording distinct reduction products depending on the nature of the reductant. With Et3SiH, a number of aliphatic and aromatic aldehydes are reduced into symmetric ethers, while iPr3SiH yielded silylated alcohols. Studies of the reaction mechanism led to the isolation of aldehyde/uranyl complexes, [UO2(OTf)2(4-Me2N-PhCHO)3], [UO2(m-k2-OTf)2(PhCHO)]n and [UO2(mu-k2-OTf)(OTf)2(PhCHO)2]2 which have been fully characterized by NMR, IR and single crystal X-ray diffraction.
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cea-02269575 , version 1 (23-08-2019)

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Louis Monsigny, Pierre Thuéry, Jean-Claude Berthet, Thibault Cantat. Breaking C-O Bonds with Uranium: Uranyl Complexes as Selective Catalysts in the Hydrosilylation of Aldehydes. ACS Catalysis, 2019, 9, pp.9025-9033. ⟨10.1021/acscatal.9b01408⟩. ⟨cea-02269575⟩
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