Issue 15, 2019

Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl

Abstract

Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H2, CO2, and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi–N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.

Graphical abstract: Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl

Supplementary files

Article information

Article type
Edge Article
Submitted
17 yan 2019
Accepted
27 fev 2019
First published
28 fev 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 4169-4176

Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl

J. Ramler, J. Poater, F. Hirsch, B. Ritschel, I. Fischer, F. M. Bickelhaupt and C. Lichtenberg, Chem. Sci., 2019, 10, 4169 DOI: 10.1039/C9SC00278B

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