Issue 98, 2021

Experimental and theoretical evidence of attractive interactions between dianions: [PdCl4]2−⋯[PdCl4]2−

Abstract

Inspection of the arrangement of tetrachloridopalladate(II) centers in a crystalline solid places the Cl of one [PdCl4]2− directly above the Pd center of its neighbor. A survey of the CSD provides 22 more examples of such MX42−⋯MX42− complexes, with M being a Group 10 metal and X = Cl, Br, or I. Quantum calculations attribute this arrangement to a π-hole bond wherein Cl lone pairs of one unit transfer charge to vacant orbitals above the Pd center of its neighbor. The stabilizing effect of this bond must overcome the strong Coulombic repulsion between the two dianions, which is facilitated by a polarizable environment as would be present in a crystal, but much more so when the effects of the neighboring counterions are factored in. These conclusions are extended to other [MX4]2− homodimers, where M represents other members of Group 10, namely Ni and Pt.

Graphical abstract: Experimental and theoretical evidence of attractive interactions between dianions: [PdCl4]2−⋯[PdCl4]2−

Supplementary files

Article information

Article type
Communication
Submitted
06 Oct 2021
Accepted
09 Nov 2021
First published
15 Nov 2021
This article is Open Access
Creative Commons BY license

Chem. Commun., 2021,57, 13305-13308

Experimental and theoretical evidence of attractive interactions between dianions: [PdCl4]2−⋯[PdCl4]2−

W. Zierkiewicz, M. Michalczyk, T. Maris, R. Wysokiński and S. Scheiner, Chem. Commun., 2021, 57, 13305 DOI: 10.1039/D1CC05640A

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