Heterolytic cleavage of a Si–H bond by a metal–ligand cooperation of a cationic iridium amido complex and hydrosilylation of aldehydes

Iizuka, Kotaro; Nakajima, Yumiko; Satō, Kazuhiko

doi:10.1039/d2dt01733d

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2024

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Cited by 2 publications

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Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation

Clerc,

Humbert,

Mallet‐Ladeira

et al. 2024

ChemistryEurope

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With the aim to explore metal‐ligand cooperation across Pd−S linkages, we designed a quinoline‐based PNS tridentate ligand and prepared Pd(II) complexes thereof. Optimal solubility and stability of the dicationic complex [(PNS)Pd(II)]22+ IV2 were achieved with B(C6F5)4– as counter‐anion. It adopts a thiolate‐bridged dimeric structure with a (PdS)2 core, but readily activates hydrosilanes across the Pd−S linkage. The resulting mononuclear Pd(II) hydride [(PNSSiR3)Pd(II)H]+ VI was characterized by multi‐nuclear NMR spectroscopy and the Si−H bond coordination/activation was studied computationally. Complex IV2 was found to efficiently catalyze the hydrosilylation of alkynes, internal as well as terminal, with good stereo and regioselectivity.

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Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation

Clerc,

Humbert,

Mallet‐Ladeira

et al. 2024

ChemistryEurope

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show abstract

Reduction of C═O to CHOH by Metal Hydrides

Fernandes

2024

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering

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Heterolytic cleavage of a Si–H bond by a metal–ligand cooperation of a cationic iridium amido complex and hydrosilylation of aldehydes

Abstract: Heterolytic cleavage of a Si–H bond was achieved mediated by a metal–ligand cooperation of a cationic iridium amido complex. The reaction was applied to the catalytic hydrosilylation of benzaldehyde and its derivatives.

Cited by 2 publications

References 31 publications

Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation

Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation

Reduction of C═O to CHOH by Metal Hydrides

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