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. 2020 Oct 6;26(56):12717-12721.
doi: 10.1002/chem.202002006. Epub 2020 Sep 8.

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Ramkumar Kannan  1 , Selvakumar Balasubramaniam  1 , Sandeep Kumar  2 , Raju Chambenahalli  1 , Eluvathingal D Jemmis  2 , Ajay Venugopal  1
Affiliations

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Ramkumar Kannan et al. Chemistry. .

Abstract

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 [(Me2 NC6 H4 )Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2 NC6 H4 }Bi{OP(NMe2 )3 }3 ][B(3,5-C6 H3 Cl2 )4 ]2 . These observations led us to generate dicationic organobismuth catalyst, [(Me2 NC6 H4 )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.

Keywords: Lewis acids; bismuth; hydrosilylation; main group compounds; reactive cations.

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References

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