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- Publisher Website: 10.1073/pnas.2019265118
- Scopus: eid_2-s2.0-85099115816
- PMID: 33372160
- WOS: WOS:000607270100062
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Article: Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes
Title | Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes |
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Authors | |
Keywords | metal–metal closed-shell interaction bond theory Pauli repulsion |
Issue Date | 2021 |
Publisher | National Academy of Sciences. The Journal's web site is located at http://www.pnas.org |
Citation | Proceedings of the National Academy of Sciences, 2021, v. 118 n. 1, article no. e2019265118 How to Cite? |
Abstract | 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. |
Persistent Identifier | http://hdl.handle.net/10722/295321 |
ISSN | 2021 Impact Factor: 12.779 2020 SCImago Journal Rankings: 5.011 |
PubMed Central ID | |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Wan, Q | - |
dc.contributor.author | Yang, J | - |
dc.contributor.author | To, WP | - |
dc.contributor.author | Che, CM | - |
dc.date.accessioned | 2021-01-11T13:58:27Z | - |
dc.date.available | 2021-01-11T13:58:27Z | - |
dc.date.issued | 2021 | - |
dc.identifier.citation | Proceedings of the National Academy of Sciences, 2021, v. 118 n. 1, article no. e2019265118 | - |
dc.identifier.issn | 0027-8424 | - |
dc.identifier.uri | http://hdl.handle.net/10722/295321 | - |
dc.description.abstract | 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. | - |
dc.language | eng | - |
dc.publisher | National Academy of Sciences. The Journal's web site is located at http://www.pnas.org | - |
dc.relation.ispartof | Proceedings of the National Academy of Sciences | - |
dc.rights | Proceedings of the National Academy of Sciences. Copyright © National Academy of Sciences. | - |
dc.subject | metal–metal closed-shell interaction | - |
dc.subject | bond theory | - |
dc.subject | Pauli repulsion | - |
dc.title | Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d8 and d10 organometallic complexes | - |
dc.type | Article | - |
dc.identifier.email | Wan, Q: wendyqyw@hku.hk | - |
dc.identifier.email | Yang, J: juny@hku.hk | - |
dc.identifier.email | To, WP: kevintwp@hku.hk | - |
dc.identifier.email | Che, CM: chemhead@hku.hk | - |
dc.identifier.authority | Yang, J=rp02186 | - |
dc.identifier.authority | To, WP=rp02410 | - |
dc.identifier.authority | Che, CM=rp00670 | - |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1073/pnas.2019265118 | - |
dc.identifier.pmid | 33372160 | - |
dc.identifier.pmcid | PMC7817198 | - |
dc.identifier.scopus | eid_2-s2.0-85099115816 | - |
dc.identifier.hkuros | 320795 | - |
dc.identifier.volume | 118 | - |
dc.identifier.issue | 1 | - |
dc.identifier.spage | article no. e2019265118 | - |
dc.identifier.epage | article no. e2019265118 | - |
dc.identifier.isi | WOS:000607270100062 | - |
dc.publisher.place | United States | - |