title: Complexes between hypohalous acids and phosphine derivatives. Pnicogen bond versus halogen bond versus hydrogen bond.
abstract: The complexes of HOBr:PH2Y (Y=H, F, Cl, Br, CH3, NH2, OH, and NO2), HOCl:PH2F, and HOI:PH2F have been investigated with ab initio calculations at the MP2/aug-cc-pVTZ level. Four types of structures (1, 2, 3a, and 3b) were observed for these complexes. 1 is stabilized by an O⋯P pnicogen bond, 2 by a P⋯X halogen bond, 3a by a H⋯P hydrogen bond and a P⋯X pnicogen bond, and 3b by H⋯P and H⋯Br hydrogen bonds. Their relative stability is related to the halogen X of HOX and the substituent Y of PH2Y. These structures can compete with interaction energy of -10.22∼-29.40 kJ/mol. The HO stretch vibration shows a small red shift in 1, a small irregular shift in 2, but a prominent red shift in 3a and 3b. The XO stretch vibration exhibits a smaller red shift in 1, a larger red shift in 2, but an insignificant blue shift in 3a and 3b. The PY stretch vibration displays a red shift in 1 but a blue shift in 2, 3a, and 3b. The formation mechanism, stability, and properties of these structures have been analyzed with molecular electrostatic potentials, orbital interactions, and non-covalent interaction index.
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
authors.forename: Qingzhong
authors.initials: Q
authors.lastname: Li
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
authors.forename: Hongjie
authors.initials: H
authors.lastname: Zhu
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
authors.forename: Hongying
authors.initials: H
authors.lastname: Zhuo
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
authors.forename: Xin
authors.initials: X
authors.lastname: Yang
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China.
authors.forename: Wenzuo
authors.initials: W
authors.lastname: Li
authors.affiliation: The Laboratory of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, People's Republic of China. Electronic address: jbchengyt@sohu.com.
authors.forename: Jianbo
authors.initials: J
authors.lastname: Cheng
mesh_terms: D006219:Halogens / Q000737:chemistry*; D006860:Hydrogen Bonding; D010720:Phosphines / Q000737:chemistry*; D055672:Static Electricity; D013816:Thermodynamics
chemical_list: D006219:Halogens; D010720:Phosphines; C044646:phosphine
keywords: Halogen bonds; Hydrogen bonds; Hypohalous acids; Phosphine derivatives; Pnicogen bonds