期刊
INORGANIC CHEMISTRY FRONTIERS
卷 9, 期 8, 页码 1655-1665出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2qi00034b
关键词
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资金
- Russian Science Foundation [19-13-00013]
- MICIU/AEI of Spain [PID2020-115637GB-I00]
- Russian Science Foundation [19-13-00013] Funding Source: Russian Science Foundation
This study discovered a novel mechanism for the formation of bifurcated mu(2)-XMIDLINE HORIZONTAL ELLIPSIS(C,C) halogen bonds, induced by the nucleophilic properties of two Cu-I-bound isocyanide groups. The theoretical calculations further confirmed the nature of this bonding.
In the structures of the isostructural cocrystals [CuI3(CNXyl)(3)]center dot 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 pi-donating d(10)[Cu-I] center and function as an integrated two-center halogen bond acceptor forming bifurcated mu(2)-XMIDLINE HORIZONTAL ELLIPSIS(C,C) halogen bonds. This bonding includes the electronegative regions of the two isocyanide ligands and a sigma-hole of an X center of CHX3 and it is not supported by any attractive XMIDLINE HORIZONTAL ELLIPSISCu interactions. The true halogen bonding nature of the mu(2)-XMIDLINE HORIZONTAL ELLIPSIS(C_-Cu-C_) 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.
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