Issue 43, 2024

Participation of transition metal atoms in noncovalent bonds

Abstract

The existence of halogen, chalcogen, pnicogen, and tetrel bonds as variants of noncovalent σ and π-hole bonds is now widely accepted, and many of their properties have been elucidated. The ability of the d-block transition metals to potentially act as Lewis acids in a similar capacity is examined systematically by DFT calculations. Metals examined span the entire range of the d-block from Group 3 to 12, and are selected from several rows of the periodic table. These atoms are placed in a variety of neutral MXn molecules, with X = Cl and O, and paired with a NH3 nucleophile. The resulting M⋯N bonds tend to be stronger than their p-block analogues, many of them with a substantial degree of covalency. The way in which the properties of these bonds is affected by the row and column of the periodic table from which the M atom is drawn, and the number and nature of ligands, is elucidated.

Graphical abstract: Participation of transition metal atoms in noncovalent bonds

Supplementary files

Article information

Article type
Paper
Submitted
26 Sep 2024
Accepted
18 Oct 2024
First published
18 Oct 2024

Phys. Chem. Chem. Phys., 2024,26, 27382-27394

Participation of transition metal atoms in noncovalent bonds

S. Scheiner, Phys. Chem. Chem. Phys., 2024, 26, 27382 DOI: 10.1039/D4CP03716B

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