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

ABSTRACT: 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.

SUBMITTER: Brands MB

PROVIDER: S-EPMC5842375 | biostudies-literature | 2018 Mar

REPOSITORIES: biostudies-literature

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

Brands Maria B MB Nitsch Jörn J Guerra Célia Fonseca CF

Inorganic chemistry 20180212 5

The importance of relativity and dispersion in metallophilicity has been discussed in numerous studies. The existence of hybridization in the bonding between closed shell d<sup>10</sup>-d<sup>10</sup> 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 ...[more]

PMID: 29431436

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Project description:A number of prototypical weak electron donor-electron acceptor complexes are investigated by the Symmetry Adapted Perturbation Theory, some of which belong to novel classes of weak bonds such as halogen and chalcogen bonds. Also included are complexes involving strong Lewis acids such as BeO and AuF. The common view in the literature is to associate these novel bonds with a variety of "holes", σ, π, δ, or positive areas in their electrostatic potential maps. The presumption is that these positive areas of the electrostatic potential are indicative of the electrostatic nature of these noncovalent bonds. The electrostatic view extends to the explanations of the directionality of approaches between the subsystems forming these bonds. This work demonstrates that one common feature of these electrostatic potential "holes" is the local depletion of electron density of which the best detector is the first-order Pauli repulsion. The minimization of this repulsion determines the bond directionality and its relative angular rigidity. In relatively strong complexes of BeO with rare gases, where BeO shows a clear cavity in electron density-an ultimate "σ hole"-the electrostatic effect does not control the bending potential-the exchange repulsion does. In halogen bonds, the halogen atom is nonspherical, displaying an axial "σ hole" in its electrostatic potential. However, in no examined case, from rare gas acting as an electron donor to a polar donor to an anionic donor, is the electrostatic energy responsible for the directionality of the halogen bond. In fact, it is not even maximized in the direction of the σ hole in N2-ClF and NH3-ClF. Yet, in all the cases, the exchange repulsion is minimized in the direction of the σ hole. The minimized exchange repulsion associated with the subtle and less subtle depletions of the electron density occur on the nodal planes or on the intersections thereof in the highest occupied molecular orbitals of Lewis acids, provided that the systems are closed-shell. The role of nodal planes in covalent and coordinate covalent bonds is well recognized. This work points to their similarly equal importance in certain types of donor-acceptor noncovalent interactions.

Dataset Information

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

Publications

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

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