Some measures for making halogen bonds stronger than hydrogen bonds in H2CS-HOX (X = F, Cl, and Br) complexes.
The properties and applications of halogen bonds are dependent greatly on their strength. In this paper, we suggested some measures for enhancing the strength of the halogen bond relative to the hydrogen bond in the H(2)CS-HOX (X = F, Cl, and Br) system by means of quantum chemical calculations. It has been shown that with comparison to H(2)CO, the S electron donor in H(2)CS results in a smaller difference in strength for the Cl halogen bond and the corresponding hydrogen bond, and the Br halogen bond is even stronger than the hydrogen bond. The Li atom in LiHCS and methyl group in MeHCS cause an increase in the strength of halogen bonding and hydrogen bonding, but the former makes the halogen bond stronger and the latter makes the hydrogen bond stronger. In solvents, the halogen bond in the Br system is strong enough to compete with the hydrogen bond. The interaction nature and properties in these complexes have been analyzed with the natural bond orbital theory.
The Laboratory of Theoretical and Computational Chemistry, Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, PR China. liqingzhong1990@sina.com
Qing-Zhong
QZ
Li
Bo
B
Jing
Ran
R
Li
Zhen-Bo
ZB
Liu
Wen-Zuo
WZ
Li
Feng
F
Luan
Jian-Bo
JB
Cheng
Bao-An
BA
Gong
Jia-Zhong
JZ
Sun
D006219:Halogens / Q000737:chemistry*; D006860:Hydrogen Bonding; D008094:Lithium / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry*; D013816:Thermodynamics
D006219:Halogens; D012997:Solvents; D008094:Lithium