TY - JOUR
T1 - The electronic structure of inorganic benzenes
T2 - Valence bond and ring-current descriptions
AU - Engelberts, Jeroen J.
AU - Havenith, Remco W.A.
AU - Van Lenthe, Joop H.
AU - Jenneskens, Leonardus W.
AU - Fowler, Patrick W.
PY - 2005/7/25
Y1 - 2005/7/25
N2 - Valence bond (VB) theory and ring-current maps have been used to study the electronic structure of inorganic benzene analogues X6H6 (X = C (1), Si (2)), X6 (X = N (3), P (4)), X3Y 3H6 (X,Y = B,N (5), B,P (6), Al,N (7), Al,P (8)), and B3Y3H3 (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 B3P3H6 (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.
AB - Valence bond (VB) theory and ring-current maps have been used to study the electronic structure of inorganic benzene analogues X6H6 (X = C (1), Si (2)), X6 (X = N (3), P (4)), X3Y 3H6 (X,Y = B,N (5), B,P (6), Al,N (7), Al,P (8)), and B3Y3H3 (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 B3P3H6 (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.
UR - http://www.scopus.com/inward/record.url?scp=23244453337&partnerID=8YFLogxK
U2 - 10.1021/ic050017o
DO - 10.1021/ic050017o
M3 - Article
C2 - 16022524
AN - SCOPUS:23244453337
SN - 0020-1669
VL - 44
SP - 5266
EP - 5272
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
ER -