Ramler Jacqueline, Poater Jordi, Hirsch Florian, Ritschel Benedikt, Fischer Ingo, Bickelhaupt F Matthias, Lichtenberg Crispin
Institute of Inorganic Chemistry , Julius-Maximilians Universität Würzburg , Am Hubland , 97074 Würzburg , Germany . Email:
ICREA , Pg. Lluís Companys 23 , 08010 Barcelona , Spain.
Chem Sci. 2019 Feb 28;10(15):4169-4176. doi: 10.1039/c9sc00278b. eCollection 2019 Apr 21.
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.
最近，第五和第六周期重p区元素化合物的化学领域取得了重大进展，揭示了其对诸如H、CO和乙烯等小分子的有趣反应模式。然而，迄今为止，尚未报道该领域中与一氧化碳（该领域的基准底物之一）发生的明确、均相的插入反应。我们在此证明，一种阳离子铋酰胺在温和条件下能使CO轻松插入Bi-N键。这种方法首次直接获得了阳离子铋氨基甲酰基物种。通过NMR、IR和UV/vis光谱、元素分析、单晶X射线分析、循环伏安法和DFT计算对其进行表征，揭示了其有趣的性质，例如铋中心的可逆电子转移以及在353 nm处的吸收特征，该吸收特征归因于涉及铋-氨基甲酰基官能团的σ和π型轨道的跃迁。实验和理论相结合的方法深入了解了CO插入的机理。底物范围可以扩展到异腈。
