期刊
CHEMICAL SCIENCE
卷 10, 期 15, 页码 4169-4176出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9sc00278b
关键词
-
资金
- Fonds der Chemischen Industrie
- DFG [GRK 2112]
- Netherlands Organization for Scientific Research (NWO)
- Catalan Government [2017SGR348]
- Spanish MINECO [CTQ2016-77558-R, MDM-2017-0767]
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, 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 sigma- and -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.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据