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Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Kannan, R and Balasubramaniam, S and Kumar, S and Chambenahalli, R and Jemmis, ED and Venugopal, A (2020) Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation. In: Chemistry - A European Journal, 26 (56). pp. 12717-12721.

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Official URL: https://doi.org/10.1002/chem.202002006


Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si−H addition. © 2020 Wiley-VCH GmbH

Item Type: Journal Article
Publication: Chemistry - A European Journal
Publisher: Wiley-VCH Verlag
Additional Information: The copyright for this article belongs to Wiley-VCH Verlag.
Keywords: Aldehydes; Bismuth metallography; Catalysis; Hydrosilylation; Ketones; Metal complexes; Nuclear magnetic resonance spectroscopy; Single crystals; Transition metal compounds; Transition metals, Carbonyl activation; Computational analysis; Electron-deficient; Electrophilic site; High yield; Homogeneous catalysis; Silyl ethers; Single crystal x-ray diffraction, Bismuth compounds
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 13 Feb 2023 04:11
Last Modified: 13 Feb 2023 04:11
URI: https://eprints.iisc.ac.in/id/eprint/80195

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