Xu Shuo, Wan Qingyun, Yang Jun, Che Chi-Ming
Department of Chemistry, State Kay Laboratory of Synthetic Chemistry, and CAS-HKU Joint Laboratory on New Materials, The University of Hong Kong, Pokfulam Road, Hong Kong, China.
HKU Shenzhen Institute of Research & Innovation, Shenzhen 518057, China.
J Phys Chem Lett. 2024 Feb 29;15(8):2193-2201. doi: 10.1021/acs.jpclett.3c03434. Epub 2024 Feb 19.
Metallophilicity has been widely considered to be the driving force for self-assembly of closed-shell d metal complexes, but this view has been challenged by recent studies showing that metallophilicity in linear d-d dimers is repulsive. This is due to strong metal-metal (M-M') Pauli repulsion (Wan, Q., 2021, 118, e2019265118). Here, we study M-M' Pauli repulsion in d metal clusters. Our results show that M-M' Pauli repulsion in d polynuclear clusters is 6-52% weaker than in similar linear d complexes due to the anisotropic shape of (+1)s-d hybridized orbitals. The overall M-M' interactions in closed-shell d polynuclear metal clusters remain repulsive. The effects of coordination geometry, relativistic effects, and the ligand's electronegativity on M-M' Pauli repulsion in polynuclear d clusters have been explored. These findings provide valuable guidance for the design and development of ligands and coordination geometries that alleviate M-M' Pauli repulsion in d metal cluster systems.
金属亲合性一直被广泛认为是闭壳层d金属配合物自组装的驱动力，但最近的研究表明线性d-d二聚体中的金属亲合性具有排斥作用，这一观点受到了挑战。这是由于强烈的金属-金属（M-M'）泡利排斥作用（万强，2021，118，e2019265118）。在此，我们研究了d金属簇中的M-M'泡利排斥作用。我们的结果表明，由于（+1）s-d杂化轨道的各向异性形状，d多核簇中的M-M'泡利排斥作用比类似的线性d配合物弱6%-52%。闭壳层d多核金属簇中的整体M-M'相互作用仍然是排斥性的。我们还探讨了配位几何、相对论效应和配体电负性对多核d簇中M-M'泡利排斥作用的影响。这些发现为设计和开发减轻d金属簇体系中M-M'泡利排斥作用的配体和配位几何提供了有价值的指导。
