Metallophilic interaction

In chemistry, a metallophilic interaction is defined as a type of non-covalent attraction between heavy metal atoms. The atoms are often within Van der Waals distance of each other and are about as strong as hydrogen bonds.^[1] The effect can be intramolecular or intermolecular. Intermolecular metallophilic interactions can lead to formation of supramolecular assemblies whose properties vary with the choice of element and oxidation states of the metal atoms and the attachment of various ligands to them.^[2]

The nature of such interactions remains the subject of vigorous debate with recent studies emphasizing that the metallophilic interaction is repulsive due to strong metal-metal Pauli exclusion principle repulsion.^[3]

^ Hunks, William J.; Jennings, Michael C.; Puddephatt, Richard J. (2002). "Supramolecular Gold(I) Thiobarbiturate Chemistry: Combining Aurophilicity and Hydrogen Bonding to Make Polymers, Sheets, and Networks". Inorg. Chem. 41 (17): 4590–4598. doi:10.1021/ic020178h. PMID 12184779.
^ Assadollahzadeh, Behnam; Schwerdtfeger, Peter (2008). "A comparison of metallophilic interactions in group 11[X–M–PH₃]_n (n = 2–3) complex halides (M = Cu, Ag, Au; X = Cl, Br, I) from density functional theory". Chemical Physics Letters. 462 (4–6): 222–228. Bibcode:2008CPL...462..222A. doi:10.1016/j.cplett.2008.07.096.
^ Wan, Qingyun; Yang, Jun; To, Wai-Pong; Che, Chi-Ming (2021-01-05). "Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d 8 and d 10 organometallic complexes". Proceedings of the National Academy of Sciences. 118 (1): e2019265118. doi:10.1073/pnas.2019265118. ISSN 0027-8424. PMC 7817198. PMID 33372160.

[1] Hunks, William J.; Jennings, Michael C.; Puddephatt, Richard J. (2002). "Supramolecular Gold(I) Thiobarbiturate Chemistry: Combining Aurophilicity and Hydrogen Bonding to Make Polymers, Sheets, and Networks". Inorg. Chem. 41 (17): 4590–4598. doi:10.1021/ic020178h. PMID 12184779.

[comparison-2] Assadollahzadeh, Behnam; Schwerdtfeger, Peter (2008). "A comparison of metallophilic interactions in group 11[X–M–PH₃]_n (n = 2–3) complex halides (M = Cu, Ag, Au; X = Cl, Br, I) from density functional theory". Chemical Physics Letters. 462 (4–6): 222–228. Bibcode:2008CPL...462..222A. doi:10.1016/j.cplett.2008.07.096.

[:0-3] Wan, Qingyun; Yang, Jun; To, Wai-Pong; Che, Chi-Ming (2021-01-05). "Strong metal–metal Pauli repulsion leads to repulsive metallophilicity in closed-shell d 8 and d 10 organometallic complexes". Proceedings of the National Academy of Sciences. 118 (1): e2019265118. doi:10.1073/pnas.2019265118. ISSN 0027-8424. PMC 7817198. PMID 33372160.

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