new unconventional halogen bond C----X···H----M between HCCX (X = Cl and Br) and HMH (M = Be and Mg): An ab initio study

In this article, a new type of halogen-bonded complex YCCX···HMY (X = Cl, Br; M = Be, Mg; Y = H, F, CH₃) has been predicted and characterized at the MP2/aug-cc-pVTZ level. We named it as halogen-hydride halogen bonding. In each YCCX···HMY complex, a halogen bond is formed between the positively char...

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Bibliographic Details
Published in:Journal of computational chemistry 2010-06, Vol.31 (8), p.1662-1669
Main Authors: Li, Qing-Zhong, Dong, Xu, Jing, Bo, Li, Wen-Zuo, Cheng, Jian-Bo, Gong, Bao-An, Yu, Zhi-Wu
Format: Article
Language:English
Subjects:
AIM
dihydrogen bond
halogen bond
halogen-hydride halogen bond
NBO
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Summary:In this article, a new type of halogen-bonded complex YCCX···HMY (X = Cl, Br; M = Be, Mg; Y = H, F, CH₃) has been predicted and characterized at the MP2/aug-cc-pVTZ level. We named it as halogen-hydride halogen bonding. In each YCCX···HMY complex, a halogen bond is formed between the positively charged X atom and the negatively charged H atom. This new kind of halogen bond has similar characteristics to the conventional halogen bond, such as the elongation of the C---X bond and the red shift of the C---X stretch frequency upon complexation. The interaction strength of this type of halogen bond is in a range of 3.34-10.52 kJ/mol, which is smaller than that of dihydrogen bond and conventional halogen bond. The nature of the electrostatic interaction in this type of halogen bond has also been unveiled by means of the natural bond orbital, atoms in molecules, and energy decomposition analyses.
ISSN:0192-8651
1096-987X
DOI:10.1002/jcc.21451