TY  - JOUR
A1  - Ramler, Jacqueline
A1  - Poater, Jordi
A1  - Hirsch, Florian
A1  - Ritschel, Benedikt
A1  - Fischer, Ingo
A1  - Bickelhaupt, F. Matthias
A1  - Lichtenberg, Crispin
T1  - Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl
JF  - Chemical Science
N2  - 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.
KW  - carbon monoxide
KW  - p-block element
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-181627
VL  - 10
ER  -