In the structures of the isostructural cocrystals[Cu^(I)_(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...In the structures of the isostructural cocrystals[Cu^(I)_(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 aπ-donating d10[Cu^(I)]center and function as an integrated two-center halogen bond acceptor forming bifurcatedμ_(2)-X⋯(C,C)halogen bonds.展开更多
Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along w...Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along with gradual accumulation of iodine,namely[Cu(I_(3))(CNXyl)_(3)](two crystalline polymorphs 2^(Ⅰ) and 2^(Ⅱ)),[Cu(I_(3))(CNXyl)_(3)]·1/2I_(2)(2·1/2 I_(2))and[Cu(CNXyl)_(3)](I_(5))(3);all these compounds were studied by X-ray diffractometry.Molecular electrostatic potential(MEP)surface plots were also calculated using density functional theory(DFT)for isolated molecules of 2 and I_(2),showing electrophilic and nucleophilic sites.Halogen bonding in 2·1/2 I_(2) was additionally elucidated for both crystal and cluster models,including combined quantum theory of atoms-in-molecules(QTAIM)and one-electron potential(OEP)projections.For model clusters,DFT energetic analysis,quantum theory of atoms-in-molecules,combined with the noncovalent interaction index plot(QTAIM/NCIplot),natural bond orbital(NBO)donor–acceptor charge transfer analysis,and Wiberg bond index(WBI)analysis were used.In the structure of 2·1/2I_(2),the presence of an I_(2)…I_(3)_(−)halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I_(5)^(−)(and then I_(8)^(2−))ligands from I_(2) and metal-coordinated I_(3)_(−).展开更多
基金funded by the Russian Science Foundation(project 19-13-00013)Measurements were performed at the Center for Magnetic Resonance,Center for X-ray Diffraction Studies,Center for Chemical Analysis and Materials Research,and Chemistry Educational Center(all belonging to Saint Petersburg State University).A.F.thanks the MICIU/AEI of Spain(project PID2020-115637GB-I00,FEDER funds)for financial support of these theoretical studies.
文摘In the structures of the isostructural cocrystals[Cu^(I)_(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 aπ-donating d10[Cu^(I)]center and function as an integrated two-center halogen bond acceptor forming bifurcatedμ_(2)-X⋯(C,C)halogen bonds.
基金supported by the Russian Science Foundation projects 22-13-00078(experimental part and XRD analysis)22-73-00021(theoretical calculations under periodic conditions and for cluster mode)The QTAIM/NCIPlot calculations were funded by the MICIU/AEI of Spain(project PID2020-115637GB-I00 FEDER funds)。
文摘Crystallization of[CuI(CNXyl)_(3)](1)with I_(2)(exhibiting strong halogen bond donor properties),at different molar ratios between the reactants,resulted in a series of(XylNC)Cu^(Ⅰ) crystal polyiodides formed along with gradual accumulation of iodine,namely[Cu(I_(3))(CNXyl)_(3)](two crystalline polymorphs 2^(Ⅰ) and 2^(Ⅱ)),[Cu(I_(3))(CNXyl)_(3)]·1/2I_(2)(2·1/2 I_(2))and[Cu(CNXyl)_(3)](I_(5))(3);all these compounds were studied by X-ray diffractometry.Molecular electrostatic potential(MEP)surface plots were also calculated using density functional theory(DFT)for isolated molecules of 2 and I_(2),showing electrophilic and nucleophilic sites.Halogen bonding in 2·1/2 I_(2) was additionally elucidated for both crystal and cluster models,including combined quantum theory of atoms-in-molecules(QTAIM)and one-electron potential(OEP)projections.For model clusters,DFT energetic analysis,quantum theory of atoms-in-molecules,combined with the noncovalent interaction index plot(QTAIM/NCIplot),natural bond orbital(NBO)donor–acceptor charge transfer analysis,and Wiberg bond index(WBI)analysis were used.In the structure of 2·1/2I_(2),the presence of an I_(2)…I_(3)_(−)halogen bonded linkage gives a key toward the understanding of the precise mechanism for the generation of I_(5)^(−)(and then I_(8)^(2−))ligands from I_(2) and metal-coordinated I_(3)_(−).
