Aromatic changes in isoelectronic derivatives of phenalenyl radicals by central carbon replacement

Goar Sánchez-Sanz; Cristina Trujillo; Ibon Alkorta; José Elguero

doi:10.1016/j.tet.2016.06.050

Aromatic changes in isoelectronic derivatives of phenalenyl radicals by central carbon replacement

Goar Sánchez-Sanz, Cristina Trujillo, Ibon Alkorta, José Elguero

CSIC - Instituto de Química Médica

Research output: Contribution to journal › Article › peer-review

Abstract

A computational study of the aromatic characteristics of phenalenyl (PLY) upon replacement of the central carbon atom by Si, Ge, N, P, As, B, Al and Ga atoms comprising isoelectronic series with different charges (0, +1, −1) has been performed at the B3LYP/6-311++G(d,p) level. Two different geometries have been obtained, one planar and another one bowl-shaped. PLY derivatives exhibit a loss of the aromatic character in all cases indicated by NICS (Nucleus-Independent Chemical Shifts) values. These aromatic features are also in agreement with the pyramidalisation undergone by the central atom. The current density maps for those planar systems corroborate NICS findings. These variations in the aromaticity have been rationalised in terms of charge localisation. Harmonic oscillator model of aromaticity (HOMA) and para-delocalisation indices (PDI) have been used to evaluate the electron density delocalisation. HOMA values do not correlate with NICS but PDI indices follow the same trend than NICS.

Original language	English
Pages (from-to)	4690-4699
Number of pages	10
Journal	Tetrahedron
Volume	72
Issue number	31
Early online date	22 Jun 2016
DOIs	https://doi.org/10.1016/j.tet.2016.06.050
Publication status	Published - 4 Aug 2016

Keywords

aromaticity
Icosagen
NICS
Phenalenyl
Pnictogen
Tetrel
Wiberg bond indices

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10.1016/j.tet.2016.06.050

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title = "Aromatic changes in isoelectronic derivatives of phenalenyl radicals by central carbon replacement",

abstract = "A computational study of the aromatic characteristics of phenalenyl (PLY) upon replacement of the central carbon atom by Si, Ge, N, P, As, B, Al and Ga atoms comprising isoelectronic series with different charges (0, +1, −1) has been performed at the B3LYP/6-311++G(d,p) level. Two different geometries have been obtained, one planar and another one bowl-shaped. PLY derivatives exhibit a loss of the aromatic character in all cases indicated by NICS (Nucleus-Independent Chemical Shifts) values. These aromatic features are also in agreement with the pyramidalisation undergone by the central atom. The current density maps for those planar systems corroborate NICS findings. These variations in the aromaticity have been rationalised in terms of charge localisation. Harmonic oscillator model of aromaticity (HOMA) and para-delocalisation indices (PDI) have been used to evaluate the electron density delocalisation. HOMA values do not correlate with NICS but PDI indices follow the same trend than NICS.",

keywords = "aromaticity, Icosagen, NICS, Phenalenyl, Pnictogen, Tetrel, Wiberg bond indices",

author = "Goar S{\'a}nchez-Sanz and Cristina Trujillo and Ibon Alkorta and Jos{\'e} Elguero",

note = "Funding Information: We thank the Ministerio de Ciencia e Innovaci{\'o}n (Project No. CTQ2015-63997-C2-2-P) and the Comunidad Aut{\'o}noma de Madrid (Project FOTOCARBON, ref S2013/MIT-2841) for continuous support. Thanks are given to the CTI (CSIC), to Irish Centre for High-End Computing (ICHEC) and the Trinity Center for High-Performance Computing (TCHPC) for the provision of computational facilities. G.S.-S. wants to thank to Human Frontier Science Program (Project Reference: LT001022/2013-C) for the support. Publisher Copyright: {\textcopyright} 2016 Elsevier Ltd",

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AU - Sánchez-Sanz, Goar

AU - Trujillo, Cristina

AU - Alkorta, Ibon

AU - Elguero, José

N1 - Funding Information: We thank the Ministerio de Ciencia e Innovación (Project No. CTQ2015-63997-C2-2-P) and the Comunidad Autónoma de Madrid (Project FOTOCARBON, ref S2013/MIT-2841) for continuous support. Thanks are given to the CTI (CSIC), to Irish Centre for High-End Computing (ICHEC) and the Trinity Center for High-Performance Computing (TCHPC) for the provision of computational facilities. G.S.-S. wants to thank to Human Frontier Science Program (Project Reference: LT001022/2013-C) for the support. Publisher Copyright: © 2016 Elsevier Ltd

PY - 2016/8/4

Y1 - 2016/8/4

N2 - A computational study of the aromatic characteristics of phenalenyl (PLY) upon replacement of the central carbon atom by Si, Ge, N, P, As, B, Al and Ga atoms comprising isoelectronic series with different charges (0, +1, −1) has been performed at the B3LYP/6-311++G(d,p) level. Two different geometries have been obtained, one planar and another one bowl-shaped. PLY derivatives exhibit a loss of the aromatic character in all cases indicated by NICS (Nucleus-Independent Chemical Shifts) values. These aromatic features are also in agreement with the pyramidalisation undergone by the central atom. The current density maps for those planar systems corroborate NICS findings. These variations in the aromaticity have been rationalised in terms of charge localisation. Harmonic oscillator model of aromaticity (HOMA) and para-delocalisation indices (PDI) have been used to evaluate the electron density delocalisation. HOMA values do not correlate with NICS but PDI indices follow the same trend than NICS.

AB - A computational study of the aromatic characteristics of phenalenyl (PLY) upon replacement of the central carbon atom by Si, Ge, N, P, As, B, Al and Ga atoms comprising isoelectronic series with different charges (0, +1, −1) has been performed at the B3LYP/6-311++G(d,p) level. Two different geometries have been obtained, one planar and another one bowl-shaped. PLY derivatives exhibit a loss of the aromatic character in all cases indicated by NICS (Nucleus-Independent Chemical Shifts) values. These aromatic features are also in agreement with the pyramidalisation undergone by the central atom. The current density maps for those planar systems corroborate NICS findings. These variations in the aromaticity have been rationalised in terms of charge localisation. Harmonic oscillator model of aromaticity (HOMA) and para-delocalisation indices (PDI) have been used to evaluate the electron density delocalisation. HOMA values do not correlate with NICS but PDI indices follow the same trend than NICS.

KW - aromaticity

KW - Icosagen

KW - NICS

KW - Phenalenyl

KW - Pnictogen

KW - Tetrel

KW - Wiberg bond indices

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DO - 10.1016/j.tet.2016.06.050

M3 - Article

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SN - 0040-4020

VL - 72

SP - 4690

EP - 4699

JO - Tetrahedron

JF - Tetrahedron

IS - 31

ER -

Aromatic changes in isoelectronic derivatives of phenalenyl radicals by central carbon replacement

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