Journal
CHEMPHYSCHEM
Volume 22, Issue 22, Pages 2281-2285Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.202100681
Keywords
anion-anion interaction; group 7; matere bond; noncovalent interaction; sigma-hole
Funding
- MICIU/AEI of Spain (FEDER funds) [CTQ2017-85821-R]
- Politecnico di Milano within the CRUI-CARE Agreement
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Experimental and theoretical evidence suggests that interactions between electron rich atoms and tetroxide anions of group 7 elements involve a new type of attractive sigma-hole interactions, leading to the formation of supramolecular anionic dimers or polymers. These interactions are categorized as matere bonds (MaB) and distinguished from classical metal-ligand coordination bonds.
In this communication experimental and theoretical results are reported affording strong evidence that interactions between electron rich atoms and the metal of tetroxide anions of group 7 elements are a new case of attractive and sigma-hole interactions. Single crystal X-ray analyses, molecular electrostatic potentials, quantum theory of atoms-in-molecules, and noncovalent interaction plot analyses show that in crystalline permanganate and perrhenate salts the metal in Mn/ReO4- anion can act as electron acceptors, the oxygen of another Mn/ReO4- anion can act as the donor and supramolecular anionic dimers or polymers are formed. The name matere bond (MaB) is proposed to categorize these noncovalent interactions and to differentiate them from the classical metal-ligand coordination bond.
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