摘要
Iodine-involved single-electron halogen bonds (SEXBs) weak interactions in the systems of CH3···I-Y(Y = BH2, H, CH3, CH==CH2, C≡CH, CN, NC) were investigated for the first time using B3LYP/6-311++G(d,p) and MP2/aug-cc-pVTZ computational levels (the relativistic effective core potential basis set of Lanl2dz was used on iodine atom). The interaction energies between two moieties with basis set super-position error corrections for the seven complexes are -0.57, -1.36, -3.80, -2.17, -4.49,-6.33 and -8.64 kJ mol-1 (MP2/aug-cc-pVTZ ), respectively, which shows that SEXBs interactions are all weak. Natural bond orbital theory analysis revealed that charges flow from CH3 to the I-Y moiety. The total amount of natural bond orbital charge transfer (ΔNC) from the CH3 radical to I-Y increases in the order CH3…IBH2 < CH3…IH ≈ CH3…ICH3 ≈ CH3···IC2H3 < CH3…ICCH< CH3…ICN< CH3…INC. Atoms-in-molecules theory was used to investigate the topological properties of the bond critical points in the seven SEXB structures.
Iodine-involved single-electron halogen bonds （SEXBs） weak interactions in the systems of CH3…I--Y（Y = BH2, H, CH3, CH=CH〉 C≡CH, CN, NC） were investigated for the first time using B3LYP/6-31 l＋＋G（d,p） and MP2/aug-cc-pVTZ computational levels （the relativistic effective core potential basis set of Lanl2dz was used on iodine atom）. The interaction energies be- tween two moieties with basis set super-position error corrections for the seven complexes are -0.57, -1.36, -3.80, -2.17, -4.49, -6.33 and -8.64 kJ mo1-1 （MP2/aug-cc-pVTZ）, respectively, which shows that SEXBs interactions are all weak. Natural bond orbital theory analysis revealed that charges flow from CH3 to the I--Y moiety. The total amount of natural bond orbital charge transfer （ANc） from the CH3 radical to I--Y increases in the order CH3..-IBH2 〈 CH3…IH ≈ CH3…ICH3 ≈ CH3…IC2H3 〈 CH3...ICCH 〈 CH3…-ICN 〈 CH3…INC. Atoms-in-molecules theory was used to investigate the topological properties of the bond critical points in the seven SEXB structures.
基金
supported by the Key Project of the Chinese Ministry of Education(211189)
the National Natural Science Foundation of China(51063006)
the"QingLan"Talent Engineering Funds of Tianshui Normal University
关键词
CH3自由基
弱相互作用
碘原子
单电子
债券
C2H3
点数
系统
CH3 radical, single-electron iodine-bond, natural bond orbital analysis, electron density topological property
