TY - JOUR
T1 - An insight on the aromatic changes in closed shell icosagen, tetrel, and pnictogen phenalenyl derivatives
AU - Trujillo, Cristina
AU - Sánchez-Sanz, Goar
AU - Alkorta, Ibon
AU - Elguero, José
N1 - Funding Information:
Thanks are given to the Human Frontier Science Program (Project Reference: LT001022/2013-C) for the support and to the Irish Centre for High-End Computing (ICHEC) and Centro de Computación Científica de la Universidad Autónoma de Madrid (CCC-UAM) for the provision of computational facilities. This work has been supported by the Spanish Ministerio de Economía y Competitividad (CTQ2015-63997-C2-2-P) and Comunidad Autónoma de Madrid (S2013/MIT-2841, Fotocarbon). Computer, storage and other resources from the CTI (CSIC) are gratefully acknowledged.
Publisher Copyright:
© 2016, Springer Science+Business Media New York.
PY - 2017/4/1
Y1 - 2017/4/1
N2 - A computational study of the aromatic and antiaromatic characteristics of closed shell charged phenalenyl (PLY+1 and PLY−1) upon replacement of the central carbon atom by icosagen (B, Al and Ga), tetrel (Si and Ge) and pnictogen (N, P and As) atoms comprising systems in which the icosagen and pnictogen derivatives considered are neutral while the tetrel ones are anions or cations, has been carried out at the B3LYP/6–311++G(d,p) computational level. By substitution, two different kinds of structures have been obtained, one planar (N and B) and another one bowl-shaped depending on the size of the central atom. In terms of aromaticity, the substitution of the central C atom causes a loss of the aromatic character in all cases as indicated by nucleus-independent chemical shifts (NICS) profiles and NICS values on the 0.001 au isosurface. Regarding the charge, PLY+1 presents larger electron delocalisation than PLY−1, phenomenon associated with aromaticity. Furthermore, the current density maps for those planar systems corroborate NICS findings, showing anticlockwise currents in PLY+1 (like in benzene) but clockwise in PLY-N0 and PLY-B0, indicating aromatic and antiaromatic behaviour, respectively.
AB - A computational study of the aromatic and antiaromatic characteristics of closed shell charged phenalenyl (PLY+1 and PLY−1) upon replacement of the central carbon atom by icosagen (B, Al and Ga), tetrel (Si and Ge) and pnictogen (N, P and As) atoms comprising systems in which the icosagen and pnictogen derivatives considered are neutral while the tetrel ones are anions or cations, has been carried out at the B3LYP/6–311++G(d,p) computational level. By substitution, two different kinds of structures have been obtained, one planar (N and B) and another one bowl-shaped depending on the size of the central atom. In terms of aromaticity, the substitution of the central C atom causes a loss of the aromatic character in all cases as indicated by nucleus-independent chemical shifts (NICS) profiles and NICS values on the 0.001 au isosurface. Regarding the charge, PLY+1 presents larger electron delocalisation than PLY−1, phenomenon associated with aromaticity. Furthermore, the current density maps for those planar systems corroborate NICS findings, showing anticlockwise currents in PLY+1 (like in benzene) but clockwise in PLY-N0 and PLY-B0, indicating aromatic and antiaromatic behaviour, respectively.
KW - Aromaticity
KW - Icosagen
KW - NICS
KW - Phenalenyl
KW - Pnictogen
KW - Tetrel
KW - Wiberg bond indices
UR - http://www.scopus.com/inward/record.url?scp=84997521985&partnerID=8YFLogxK
U2 - 10.1007/s11224-016-0882-y
DO - 10.1007/s11224-016-0882-y
M3 - Article
AN - SCOPUS:84997521985
SN - 1040-0400
VL - 28
SP - 345
EP - 355
JO - Structural Chemistry
JF - Structural Chemistry
IS - 2
ER -