Carbon monoxide insertion at a heavy p-block element: unprecedented formation of a cationic bismuth carbamoyl
Please always quote using this URN: urn:nbn:de:bvb:20-opus-181627
- 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 bismuthMajor 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.…
Author: | Jacqueline Ramler, Jordi PoaterORCiD, Florian Hirsch, Benedikt Ritschel, Ingo FischerORCiD, F. Matthias BickelhauptORCiD, Crispin LichtenbergORCiD |
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URN: | urn:nbn:de:bvb:20-opus-181627 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Fakultät für Chemie und Pharmazie / Institut für Physikalische und Theoretische Chemie | |
Language: | English |
Parent Title (English): | Chemical Science |
Year of Completion: | 2019 |
Volume: | 10 |
Pagenumber: | 4169 – 4176 |
Source: | Chemical Science, 2019, 10, 4169. doi:10.1039/C9SC00278B |
DOI: | https://doi.org/10.1039/C9SC00278B |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 541 Physikalische Chemie |
Tag: | carbon monoxide; p-block element |
Release Date: | 2019/06/25 |
Licence (German): | CC BY-NC: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell |