Issue 24, 2022

On the energetic stability of halogen bonds involving metals: implications in crystal engineering

Abstract

This work reports a combined computational and experimental analysis of the ability of square planar d8 transition metal complexes to establish unconventional halogen bonding interactions with chloro-, bromo-, and iodopentafluorobenzene as σ-hole donors. Typical M⋯Ha (M = transition metal and Ha = halogen) interactions are coordination bonds (frequently halides acting as counter ions) or semicoordination bonds (neutral lone pair donor halogens). However, in recent times a new binding mode has been described in the literature with a reverse donor–acceptor role. That is, directional C–Br,I⋯M halogen bonding (HaB) interactions have been reported where the metal center acts as the electron-rich atom and the halogen atom acts as the acceptor via its σ-hole. In addition to the Cambridge Structural Database (CSD) survey of exemplifying X-ray structures, this manuscript reports a DFT study that investigates the relative ability of Ni, Pd, and Pt square planar complexes to participate in HaBs with chloro-, bromo-, and iodopentafluorobenzene.

Graphical abstract: On the energetic stability of halogen bonds involving metals: implications in crystal engineering

Supplementary files

Article information

Article type
Paper
Submitted
19 apr 2022
Accepted
04 may 2022
First published
04 may 2022

CrystEngComm, 2022,24, 4440-4446

On the energetic stability of halogen bonds involving metals: implications in crystal engineering

I. Benito, R. M. Gomila and A. Frontera, CrystEngComm, 2022, 24, 4440 DOI: 10.1039/D2CE00545J

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