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

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 , CO , and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrate...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2019-04, Vol.10 (15), p.4169-4176
Main Authors: Ramler, Jacqueline, Poater, Jordi, Hirsch, Florian, Ritschel, Benedikt, Fischer, Ingo, Bickelhaupt, F Matthias, Lichtenberg, Crispin
Format: Article
Language:English
Subjects:
Bismuth
Carbon monoxide
Cations
Chemical analysis
Crystal structure
Crystallography
Electron transfer
Infrared spectroscopy
Insertion
Mathematical analysis
NMR
Nuclear magnetic resonance
Organic chemistry
Single crystals
Substrates
X ray analysis
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Summary: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 , CO , 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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c9sc00278b