Relevance of Orbital Interactions and Pauli Repulsion in the Metal-Metal Bond of Coinage Metals

Maria B. Brands, Jörn Nitsch*, Célia Fonseca Guerra

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


The importance of relativity and dispersion in metallophilicity has been discussed in numerous studies. The existence of hybridization in the bonding between closed shell d10-d10 metal atoms has also been speculated, but the presence of attractive MO interaction in the metal-metal bond is still a matter of an ongoing debate. In this comparative study, a quantitative molecular orbital analysis and energy decomposition is carried out on the metallophilic interaction in atomic dimers (M+···M+) and molecular perpendicular [H3P-M-X]2 (where M = Cu, Ag, and Au; X = F, Cl, Br, and I). Our computational studies prove that besides the commonly accepted dispersive interactions, orbital interactions and Pauli repulsion also play a crucial role in the strength and length of the metal-metal bond. Although for M+···M+ the orbital interaction is larger than the Pauli repulsion, leading to a net attractive MO interaction, the bonding mechanism in perpendicular [H3P-M-X] dimers is different due to the larger separation between the donor and acceptor orbitals. Thus, Pauli repulsion is much larger, and two-orbital, four-electron repulsion is dominant.

Original languageEnglish
Pages (from-to)2603-2608
Number of pages6
JournalInorganic Chemistry
Issue number5
Publication statusPublished - 5 Mar 2018


J.N. thanks the DFG for a Postdoctoral Research Fellowship (NI 1737/1-1). C.F.G. thanks The Netherlands Organization for Scientific Research (NWO/CW) for financial support.

FundersFunder number
Deutsche ForschungsgemeinschaftNI 1737/1-1
Nederlandse Organisatie voor Wetenschappelijk Onderzoek


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