This paper presents a study of pnictogen bonding in a series of pyrazine•PnX5 (Pn = P, As, Sb and X = F, Cl, Br) complexes. The whole series was studied computationally. Moreover, the pyrazine complexes with PCl5 and SbCl5 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 PnX5 changed considerably upon the complex formation, which resulted in a significant change of the dipole moment of the PnX5 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.

Department of General and Inorganic Chemistry Faculty of Chemical Technology University of Pardubice Studentská 573 532 10 Pardubice Czech Republic

Faculty of Chemistry Wrocław University of Science and Technology Wybrzeże Wyspiańskiego 27 50 370 Wrocław Poland

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nam 2 166 10 Prague 6 Czech Republic

Regional Center of Advanced Technologies and Materials Department of Physical Chemistry Palacký University 77146 Olomouc Czech Republic

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