Research output: Contribution to journal › Article › peer-review
Chameleonic metal-bound isocyanides : a π-donating Cu I-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding. / Кинжалов, Михаил Андреевич; Иванов, Даниил Михайлович; Мелехова, Анна Андреевна; Бокач, Надежда Арсеньевна; Gomila, Rosa; Frontera, Antonio; Кукушкин, Вадим Юрьевич.
In: Inorganic Chemistry Frontiers, Vol. 9, No. 8, 14.02.2022, p. 1655-1665.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Chameleonic metal-bound isocyanides
T2 - a π-donating Cu I-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding
AU - Кинжалов, Михаил Андреевич
AU - Иванов, Даниил Михайлович
AU - Мелехова, Анна Андреевна
AU - Бокач, Надежда Арсеньевна
AU - Gomila, Rosa
AU - Frontera, Antonio
AU - Кукушкин, Вадим Юрьевич
N1 - Publisher Copyright: © 2022 The Royal Society of Chemistry
PY - 2022/2/14
Y1 - 2022/2/14
N2 - In the structures of the isostructural cocrystals [CuI 3(CNXyl) 3]·CHX 3 (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 μ 2-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 CHX 3 and it is not supported by any attractive X⋯Cu interactions. The true halogen bonding nature of the μ 2-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.
AB - In the structures of the isostructural cocrystals [CuI 3(CNXyl) 3]·CHX 3 (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 μ 2-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 CHX 3 and it is not supported by any attractive X⋯Cu interactions. The true halogen bonding nature of the μ 2-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.
KW - 1,4-DIIODOTETRAFLUOROBENZENE
KW - CENTER-DOT-N
KW - CO-CRYSTALS
KW - COCRYSTALS
KW - COPPER(I) COMPLEXES
KW - ELECTRON LOCALIZATION
KW - INDUCED PHOSPHORESCENCE
KW - ORBITALS
KW - THERMAL-EXPANSION
KW - TOPOLOGICAL ANALYSIS
UR - http://www.scopus.com/inward/record.url?scp=85129627218&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/99ef66b7-fe14-3e31-9620-a7c1d8f23e20/
U2 - 10.1039/d2qi00034b
DO - 10.1039/d2qi00034b
M3 - Article
VL - 9
SP - 1655
EP - 1665
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
SN - 2052-1545
IS - 8
ER -
ID: 92929059