Theoretical characterization of single-electron iodine-bond weak interactions in CHy..I--Y（Y = BH2, H, CH3, C2H3, C2H, CN, NC） systems

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 La...

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Published in中国科学通报：英文版 Vol. 57; no. 4; pp. 328 - 335
Main Author YUAN Kun LIU YanZhi ZHU YuanCheng ZUO GuoFang LUE LingLing LI ZhiFeng
Format Journal Article
LanguageEnglish
Published 2012
Subjects
C2H3
CH3自由基
债券
单电子
弱相互作用
点数
碘原子
系统
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Summary: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.
Bibliography:11-1785/N
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.
CH3 radical, single-electron iodine-bond, natural bond orbital analysis, electron density topological property
ISSN:1001-6538
1861-9541