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

Jacqueline Ramler, Jordi Poater, Florian Hirsch, Benedikt Ritschel, Ingo Fischer, F. Matthias Bickelhaupt*, Crispin Lichtenberg

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review

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 H 2 , CO 2 , 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.

Original languageEnglish
Pages (from-to)4169-4176
Number of pages8
JournalChemical Science
Volume10
Issue number15
Early online date28 Feb 2019
DOIs
Publication statusPublished - 21 Apr 2019

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