Garbagnati Anna, Seidl Michael, Balázs Gábor, Scheer Manfred
Institute of Inorganic Chemistry, University of Regensburg, 93040, Regensburg, Germany.
Chemistry. 2022 Jun 7;28(32):e202200669. doi: 10.1002/chem.202200669. Epub 2022 Apr 21.
The oxidation of [(CpMo) (μ,η :η -P )] (1) with halogens or halogen sources was investigated. The iodination afforded the ionic complexes [(CpMo) (μ,η :η -P )(μ,η :η :η :η -P I )][X] (X=I , I ) (2) and [(CpMo) (μ,η :η -P )(μ-PI )][I ] (3), while the reaction with PBr led to the complexes [(CpMo) (μ,η :η -P )(μ-Br) ][CpMoBr ] (4) [(CpMoBr) (μ,η :η -P )(μ,η -P Br )] (5) and [(CpMo) (μ-PBr )(μ-PHBr)(μ-Br) ] (6). The reaction of 1 with the far stronger oxidizing agent PCl was followed via time- and temperature-dependent P{ H} NMR spectroscopy. One of the first intermediates detected at 193 K was [(CpMo) (μ,η :η -P )(μ-PCl ) ][PCl ] (8) which rearranges upon warming to [(CpMo) (μ-PCl ) (μ-Cl) ] (9), [(CpMoCl) (μ,η :η -P )(μ-PCl )] (10) and [(CpMo) (μ,η :η -P )(μ-PCl )][CpMoCl ] (11), which could be isolated at room temperature. All complexes were characterized by single-crystal X-ray diffraction, NMR spectroscopy and their electronic structures were elucidated by DFT calculations.
研究了[(CpMo)(μ,η:η -P )] (1) 与卤素或卤素源的氧化反应。碘化反应生成离子配合物[(CpMo)(μ,η:η -P )(μ,η:η:η:η -P I )][X] (X = I , I ) (2) 和[(CpMo)(μ,η:η -P )(μ-PI )][I ] (3)，而与PBr的反应则生成配合物[(CpMo)(μ,η:η -P )(μ-Br) ][CpMoBr ] (4)、[(CpMoBr)(μ,η:η -P )(μ,η -P Br )] (5) 和[(CpMo)(μ-PBr )(μ-PHBr)(μ-Br) ] (6)。通过时间和温度依赖的P{ H} NMR光谱跟踪了1与强得多的氧化剂PCl的反应。在193 K检测到的首批中间体之一是[(CpMo)(μ,η:η -P )(μ-PCl ) ][PCl ] (8)，升温时它会重排为[(CpMo)(μ-PCl ) (μ-Cl) ] (9)、[(CpMoCl)(μ,η:η -P )(μ-PCl )] (10) 和[(CpMo)(μ,η:η -P )(μ-PCl )][CpMoCl ] (11)，这些在室温下可以分离出来。所有配合物均通过单晶X射线衍射、NMR光谱进行了表征，并通过DFT计算阐明了它们的电子结构。
