The electronic structure of inorganic benzenes: valence bond and ring-current descriptions.
Valence bond (VB) theory and ring-current maps have been used to study the electronic structure of inorganic benzene analogues X(6)H(6) (X = C (1), Si (2)), X(6) (X = N (3), P (4)), X(3)Y(3)H(6) (X,Y = B,N (5), B,P (6), Al,N (7), Al,P (8)), and B(3)Y(3)H(3) (Y = O (9), S (10)). It is shown that the homonuclear compounds possess benzene-like character, with resonance between two Kekulé-like structures and induced diatropic ring currents. Heteronuclear compounds typically show localization of the lone pairs on the electronegative atoms; Kekulé-like structures do not contribute. Of the heteronuclear compounds, only B(3)P(3)H(6) (6) has some benzene-like features with a significant contribution of two Kekulé-like structures to its VB wave function, an appreciable resonance energy, and a discernible diatropic ring current in planar geometry. However, relaxation of 6 to the optimal nonplanar chair conformation is accompanied by the onset of localization of the ring current.
Engelberts
Jeroen J
JJ
Debye Institute, Theoretical Chemistry Group, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands.
Havenith
Remco W A
RW
van Lenthe
Joop H
JH
Jenneskens
Leonardus W
LW
Fowler
Patrick W
PW
D003198:Computer Simulation; D004583:Electrons; D007287:Inorganic Chemicals / Q000737:chemistry*; D008956:Models, Chemical
D007287:Inorganic Chemicals