Pnictogen bonding in pyrazine•PnX5 (Pn = P, As, Sb and X = F, Cl, Br) complexes

• Published in: Journal of molecular modeling Vol. 23; no. 11; pp. 1 - 9
• Main Authors: Fanfrlík, Jindřich, Zierkiewicz, Wiktor, Švec, Petr, Růžičková, Zdeňka, Řezáč, Jan, Michalczyk, Mariusz, Růžička, Aleš, Michalska, Danuta, Hobza, Pavel
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.11.2017; Springer Nature B.V
• Subjects: Bonding; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Complex formation; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Dipole moments; Elongation; Molecular Medicine; Original Paper; P. Politzer 80th Birthday Festschrift; Theoretical and Computational Chemistry; X-ray crystallography; Interaction energy decomposition; Charge transfer; Pnictogen bond; Deformation energy; σ-hole magnitude
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-017-3502-x

This paper presents a study of pnictogen bonding in a series of pyrazine•PnX 5 (Pn = P, As, Sb and X = F, Cl, Br) complexes. The whole series was studied computationally. Moreover, the pyrazine complexes with PCl 5 and SbCl 5 were prepared and characterized experimentally. It was found that the Pn-N distances are only slightly elongated when compared to the sum of covalent radii. The conformation of PnX 5 changed considerably upon the complex formation, which resulted in a significant change of the dipole moment of the PnX 5 fragment and a considerably more positive σ-hole on the pnictogen atom. Finally, interaction energies were decomposed in order to provide a deeper insight into the nature of the studied pnictogen-bonded complexes. Graphical abstract The conformation of PnX5 changed considerably upon the complex formation, which resulted in a considerably more positive σ-hole on the pnictogen atom.