Wang Ding, Moutet Jules, Tricoire Maxime, Cordier Marie, Nocton Grégory
LCM, CNRS, Ecole Polytechnique, IP Paris, Route de Saclay, 91128 Palaiseau, France.
Inorganics (Basel). 2019 May;7(5):58. doi: 10.3390/inorganics7050058. Epub 2019 Apr 26.
This article presented the synthesis and characterization of original heterobimetallic species combining a divalent lanthanide fragment and a divalent nickel center bridged by the bipyrimidine ligand, a redox-active ligand. X-ray crystal structures were obtained for the Ni monomer (bipym)NiMe, , as well as the heterobimetallic dimer compounds, Cp*Yb(bipym)NiMe, , along with H solution NMR, solid-state magnetic data, and DFT calculations only for . The reactivity with CO was investigated on both compounds and the stoichiometric acetone formation is discussed based on kinetic and mechanistic studies. The key role of the lanthanide fragment was demonstrated by the relatively slow CO migratory insertion step, which indicated the stability of the intermediate.
本文介绍了由二价镧系片段和由双嘧啶配体（一种氧化还原活性配体）桥连的二价镍中心组成的新型异双金属物种的合成与表征。获得了镍单体(bipym)NiMe₂以及异双金属二聚体化合物CpYb(bipym)NiMe₂的X射线晶体结构，同时还获得了仅针对CpYb(bipym)NiMe₂的¹H溶液核磁共振、固态磁数据和密度泛函理论计算结果。研究了这两种化合物与CO的反应活性，并基于动力学和机理研究讨论了化学计量丙酮的形成。镧系片段的关键作用通过相对较慢的CO迁移插入步骤得到证明，这表明了中间体的稳定性。
