Issue 8, 2022

Chameleonic metal-bound isocyanides: a π-donating CuI-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding

Abstract

In the structures of the isostructural cocrystals [CuI3(CNXyl)3]·CHX3 (X = Br, I), two adjacent CuI-bound isocyanide groups, whose carbon lone pairs are blocked by ligation, exhibit nucleophilic properties induced by a π-donating d10[CuI] center and function as an integrated two-center halogen bond acceptor forming bifurcated μ2-X⋯(C,C) halogen bonds. This bonding includes the electronegative regions of the two isocyanide ligands and a σ-hole of an X center of CHX3 and it is not supported by any attractive X⋯Cu interactions. The true halogen bonding nature of the μ2-X⋯([C with combining low line]–Cu–[C with combining low line]) contacts was confirmed theoretically by DFT calculations using several computational tools (QTAIM, NCIplot, IRIPlot and IGMPlot indexes, MEP surfaces, ELF analysis, and electron density/electrostatic potential plots). Noncovalent interaction patterns of CNR ligands and also their metal-dependent chameleonic behavior toward noncovalent interactions were analyzed, considering the electronic properties of coordinating metal centers.

Graphical abstract: Chameleonic metal-bound isocyanides: a π-donating CuI-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding

Supplementary files

Article information

Article type
Research Article
Submitted
04 Jan 2022
Accepted
13 Feb 2022
First published
14 Feb 2022

Inorg. Chem. Front., 2022,9, 1655-1665

Chameleonic metal-bound isocyanides: a π-donating CuI-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding

M. A. Kinzhalov, D. M. Ivanov, A. A. Melekhova, N. A. Bokach, R. M. Gomila, A. Frontera and V. Yu. Kukushkin, Inorg. Chem. Front., 2022, 9, 1655 DOI: 10.1039/D2QI00034B

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