A new unconventional halogen bond CX···HM between HCCX (X = Cl and Br) and HMH (M = Be and Mg): An ab initio study

✍ Scribed by Qing-Zhong Li; Xu Dong; Bo Jing; Wen-Zuo Li; Jian-Bo Cheng; Bao-An Gong; Zhi-Wu Yu

• Book ID: 102305815
• Publisher: John Wiley and Sons
• Year: 2009
• Tongue: English
• Weight: 154 KB
• Volume: 31
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21451

✦ Synopsis

Abstract

In this article, a new type of halogen‐bonded complex YCCX···HMY (X = Cl, Br; M = Be, Mg; Y = H, F, CH~3~) 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. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010