Chameleonic metal-bound isocyanides: a π-donating CuI-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding. Issue 8 (1st March 2022)

• Record Type: Journal Article
• Authors: Kinzhalov, Mikhail A.; Ivanov, Daniil M.; Melekhova, Anna A.; Bokach, Nadezhda A.; Gomila, Rosa M.; Frontera, Antonio; Kukushkin, Vadim Yu.
• Is Part Of: Inorganic chemistry frontiers. Volume 9:Issue 8(2022)
• Page Start: 1655
• Page End: 1665
• Publication Date: 2022-03-01
• Subjects: Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d2qi00034b
• Languages: English
• ISSNs: 2052-1553

Abstract

Abstract : Two adjacent Cu I -bound isocyanide groups exhibit nucleophilic properties induced by a π-donating d 10 [Cu I ] center and function as an integrated two-center halogen bond acceptor forming bifurcated μ2 -X⋯(C, C) halogen bonds. Abstract : In the structures of the isostructural cocrystals [CuI3 (CNXyl)3 ]·CHX3 (X = Br, I), two adjacent Cu I -bound isocyanide groups, whose carbon lone pairs are blocked by ligation, exhibit nucleophilic properties induced by a π-donating d 10 [Cu I ] 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⋯(C̲–Cu–C̲) 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.