TY - JOUR
T1 - The pnictogen bond
T2 - a quantitative molecular orbital picture
AU - de Azevedo Santos, L.
AU - Hamlin, T.A.
AU - Ramalho, T.C.
AU - Bickelhaupt, F.M.
PY - 2021/6/4
Y1 - 2021/6/4
N2 - © the Owner Societies 2021.We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A−(Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A−and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.
AB - © the Owner Societies 2021.We have analyzed the structure and stability of archetypal pnictogen-bonded model complexes D3Pn⋯A−(Pn = N, P, As, Sb; D, A = F, Cl, Br) using state-of-the-art relativistic density functional calculations at the ZORA-M06/QZ4P level. We have accomplished two tasks: (i) to compute accurate trends in pnictogen-bond strength based on a set of consistent data; and (ii) to rationalize these trends in terms of detailed analyses of the bonding mechanism based on quantitative Kohn-Sham molecular orbital (KS-MO) theory in combination with a canonical energy decomposition analysis (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. We have found that pnictogen bonds have a significant covalent character stemming from strong HOMO-LUMO interactions between the lone pair of A−and σ* of D3Pn. As such, the underlying mechanism of the pnictogen bond is similar to that of hydrogen, halogen, and chalcogen bonds.
U2 - 10.1039/d1cp01571k
DO - 10.1039/d1cp01571k
M3 - Article
SN - 1463-9076
VL - 23
SP - 13842
EP - 13852
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 25
ER -