气候变化领域集成服务门户(CCPortal): Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes

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DOI	10.1073/PNAS.2019265118
	Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes
	Wan Q.; Yang J.; To W.-P.; Che C.-M.
发表日期	2021
ISSN	00278424
卷号	118 期号:1
英文摘要	Metallophilicity is defined as the interaction among closed-shell metal centers, the origin of which remains controversial, particularly for the roles of spd orbital hybridization (mixing of the spd atomic orbitals of the metal atom in the molecular orbitals of metal complex) and the relativistic effect. Our studies reveal that at close M–M′ distances in the X-ray crystal structures of d8 and d10 organometallic complexes, M–M′ closed-shell interactions are repulsive in nature due to strong M–M′ Pauli repulsion. The relativistic effect facilitates (n + 1)s-nd and (n + 1)p-nd orbital hybridization of the metal atom, where (n + 1)s-nd hybridization induces strong M–M′ Pauli repulsion and repulsive M–M′ orbital interaction, and (n + 1)p-nd hybridization suppresses M–M′ Pauli repulsion. This model is validated by both DFT (density functional theory) and high-level coupled-cluster singles and doubles with perturbative triples computations and is used to account for the fact that the intermolecular or intramolecular Ag–Ag′ distance is shorter than the Au–Au′ distance, where a weaker Ag–Ag′ Pauli repulsion plays an important role. The experimental studies verify the importance of ligands in intermolecular interactions. Although the M–M′ interaction is repulsive in nature, the linear coordination geometry of the d10 metal complex suppresses the L–L′ (ligand–ligand) Pauli repulsion while retaining the strength of the attractive L–L′ dispersion, leading to a close unsupported M–M′ distance that is shorter than the sum of the van der Waals radius (rvdw) of the metal atoms. © 2021 National Academy of Sciences. All rights reserved.
英文关键词	Bond theory; Metal–metal closed-shell interaction; Pauli repulsion
语种	英语
scopus关键词	metal complex; organometallic compound; Article; chemical phenomena; computer model; crystal structure; density functional theory; dispersion; experimental study; hybridization; metallophilicity; molecular interaction; Pauli repulsion; priority journal; synthesis; X ray
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/181123
作者单位	State Key Laboratory of Synthetic Chemistry, Department of Chemistry, University of Hong Kong, Hong Kong SAR999077, Hong Kong; Shenzhen Institute of Research and Innovation, University of Hong Kong, Shenzhen, 518053, China
推荐引用方式 GB/T 7714	Wan Q.,Yang J.,To W.-P.,等. Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes[J],2021,118(1).
APA	Wan Q.,Yang J.,To W.-P.,&Che C.-M..(2021).Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes.Proceedings of the National Academy of Sciences of the United States of America,118(1).
MLA	Wan Q.,et al."Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes".Proceedings of the National Academy of Sciences of the United States of America 118.1(2021).