Masada Koichiro, Okabe Kiyosumi, Kusumoto Shuhei, Nozaki Kyoko
Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-8656 Japan
Chem Sci. 2023 Jul 25;14(32):8524-8530. doi: 10.1039/d3sc02292g. eCollection 2023 Aug 16.
Bimetallic complexes have enabled precise control of catalysis by accumulating two discrete metal centres. In these complexes, bridging ligands are essential to combine multiple metals into one molecule. Among some bridging modes, an unsymmetric bridging mode will differentiate the electronic structures of the two metal centres. In this study, a dinuclear Rh(-i)/Rh(i) complex bridged by tridentate phosphine-phosphinine-phosphine ligands was prepared by reduction of the corresponding Rh(i) complex. Single-crystal X-ray analysis and DFT calculations suggest that the phosphinine ligands adopt an unsymmetric bridging mode wherein phosphinine accepts d-electrons from one Rh centre and, at the same time, donates lone pairs to the other Rh centre.
双金属配合物通过聚集两个离散的金属中心实现了对催化的精确控制。在这些配合物中，桥连配体对于将多种金属结合到一个分子中至关重要。在一些桥连模式中，不对称桥连模式会使两个金属中心的电子结构产生差异。在本研究中，通过还原相应的Rh(i)配合物制备了一种由三齿膦-磷杂苯-膦配体桥连的双核Rh(-i)/Rh(i)配合物。单晶X射线分析和DFT计算表明，磷杂苯配体采用不对称桥连模式，其中磷杂苯从一个Rh中心接受d电子，同时向另一个Rh中心提供孤对电子。
