The first binuclear sandwich-like complexes based on the aromatic tetraatomic species

Congzhi Wang; Nan Li; Xiuhui Zhang; Lin Ji; Qianshu Li

doi:10.1039/c1dt10508f

The first binuclear sandwich-like complexes based on the aromatic tetraatomic species

Congzhi Wang
, Nan Li^*
, Xiuhui Zhang
, Lin Ji
, Qianshu Li

^*此作品的通讯作者

Beijing Institute of Technology
Capital Normal University
South China Normal University

科研成果: 期刊稿件 › 文章 › 同行评审

4 引用（Scopus）

摘要

The first binuclear sandwich-like complexes based on the aromatic tetraatomic species with formula M₂(η⁴-E ₄)₂ (M = Al, Ga; E = N, P, As) have been studied by density functional theory (DFT). The stable conformer for each M ₂(η⁴-E₄)₂ is the staggered one with D_4d symmetry except for Ga₂(η²-N ₄)₂ with C_2v symmetry. Natural bonding orbital (NBO) analysis indicates that the metal-metal bonds of Al₂(η ⁴-E₄)₂ (E = N, P, As) and Ga ₂(η⁴-E₄)₂ (E = P, As) are all σ single bonds, which are derived mostly from the s and p_z orbitals of the metal atoms by molecular orbital (MO) analysis. For M ₂(η⁴-E₄)₂ (M = Al, Ga; E = P, As), the metal-ligand interactions are covalent, while for Al ₂(η⁴-N₄)₂ the interactions between the Al atoms and the N₄^2- ligands are ionic. According to the calculated dissociation energies for breaking metal-metal bonds, the Al-Al and Ga-Ga bonds are very strong indicating that these stable sandwich-like compounds Al₂(η⁴-E₄) ₂ (E = N, P, As) and Ga₂(η⁴-E ₄)₂ (E = P, As) may be synthesized in future experiments. The nitrogen-rich compounds Al₂(η⁴-N₄) ₂ and Ga₂(η²-N₄)₂ may be used as potential candidates of high energy density materials (HEDMs). Nucleus-independent chemical shifts (NICS) values reveal that the E ₄^2- rings in the Al₂(η⁴-E ₄)₂ (E = N, P, As) and Ga₂(η⁴- E₄)₂ (E = P, As) species possess conflicting aromaticity (σ antiaromaticity and π aromaticity) and with the same ligands, the E₄^2- ligands in Ga₂(η⁴-E ₄)₂ have more aromaticity than those in Al ₂(η⁴-E₄)₂.

源语言	英语
页（从-至）	6922-6928
页数	7
期刊	Dalton Transactions
卷	40
期	26
DOI	https://doi.org/10.1039/c1dt10508f
出版状态	已出版 - 14 7月 2011

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@article{57f0f596bc034757b88a8a882bd918ea,

title = "The first binuclear sandwich-like complexes based on the aromatic tetraatomic species",

abstract = "The first binuclear sandwich-like complexes based on the aromatic tetraatomic species with formula M2(η4-E 4)2 (M = Al, Ga; E = N, P, As) have been studied by density functional theory (DFT). The stable conformer for each M 2(η4-E4)2 is the staggered one with D4d symmetry except for Ga2(η2-N 4)2 with C2v symmetry. Natural bonding orbital (NBO) analysis indicates that the metal-metal bonds of Al2(η 4-E4)2 (E = N, P, As) and Ga 2(η4-E4)2 (E = P, As) are all σ single bonds, which are derived mostly from the s and pz orbitals of the metal atoms by molecular orbital (MO) analysis. For M 2(η4-E4)2 (M = Al, Ga; E = P, As), the metal-ligand interactions are covalent, while for Al 2(η4-N4)2 the interactions between the Al atoms and the N42- ligands are ionic. According to the calculated dissociation energies for breaking metal-metal bonds, the Al-Al and Ga-Ga bonds are very strong indicating that these stable sandwich-like compounds Al2(η4-E4) 2 (E = N, P, As) and Ga2(η4-E 4)2 (E = P, As) may be synthesized in future experiments. The nitrogen-rich compounds Al2(η4-N4) 2 and Ga2(η2-N4)2 may be used as potential candidates of high energy density materials (HEDMs). Nucleus-independent chemical shifts (NICS) values reveal that the E 42- rings in the Al2(η4-E 4)2 (E = N, P, As) and Ga2(η4- E4)2 (E = P, As) species possess conflicting aromaticity (σ antiaromaticity and π aromaticity) and with the same ligands, the E42- ligands in Ga2(η4-E 4)2 have more aromaticity than those in Al 2(η4-E4)2.",

author = "Congzhi Wang and Nan Li and Xiuhui Zhang and Lin Ji and Qianshu Li",

year = "2011",

month = jul,

day = "14",

doi = "10.1039/c1dt10508f",

language = "English",

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journal = "Dalton Transactions",

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TY - JOUR

T1 - The first binuclear sandwich-like complexes based on the aromatic tetraatomic species

AU - Wang, Congzhi

AU - Li, Nan

AU - Zhang, Xiuhui

AU - Ji, Lin

AU - Li, Qianshu

PY - 2011/7/14

Y1 - 2011/7/14

N2 - The first binuclear sandwich-like complexes based on the aromatic tetraatomic species with formula M2(η4-E 4)2 (M = Al, Ga; E = N, P, As) have been studied by density functional theory (DFT). The stable conformer for each M 2(η4-E4)2 is the staggered one with D4d symmetry except for Ga2(η2-N 4)2 with C2v symmetry. Natural bonding orbital (NBO) analysis indicates that the metal-metal bonds of Al2(η 4-E4)2 (E = N, P, As) and Ga 2(η4-E4)2 (E = P, As) are all σ single bonds, which are derived mostly from the s and pz orbitals of the metal atoms by molecular orbital (MO) analysis. For M 2(η4-E4)2 (M = Al, Ga; E = P, As), the metal-ligand interactions are covalent, while for Al 2(η4-N4)2 the interactions between the Al atoms and the N42- ligands are ionic. According to the calculated dissociation energies for breaking metal-metal bonds, the Al-Al and Ga-Ga bonds are very strong indicating that these stable sandwich-like compounds Al2(η4-E4) 2 (E = N, P, As) and Ga2(η4-E 4)2 (E = P, As) may be synthesized in future experiments. The nitrogen-rich compounds Al2(η4-N4) 2 and Ga2(η2-N4)2 may be used as potential candidates of high energy density materials (HEDMs). Nucleus-independent chemical shifts (NICS) values reveal that the E 42- rings in the Al2(η4-E 4)2 (E = N, P, As) and Ga2(η4- E4)2 (E = P, As) species possess conflicting aromaticity (σ antiaromaticity and π aromaticity) and with the same ligands, the E42- ligands in Ga2(η4-E 4)2 have more aromaticity than those in Al 2(η4-E4)2.

AB - The first binuclear sandwich-like complexes based on the aromatic tetraatomic species with formula M2(η4-E 4)2 (M = Al, Ga; E = N, P, As) have been studied by density functional theory (DFT). The stable conformer for each M 2(η4-E4)2 is the staggered one with D4d symmetry except for Ga2(η2-N 4)2 with C2v symmetry. Natural bonding orbital (NBO) analysis indicates that the metal-metal bonds of Al2(η 4-E4)2 (E = N, P, As) and Ga 2(η4-E4)2 (E = P, As) are all σ single bonds, which are derived mostly from the s and pz orbitals of the metal atoms by molecular orbital (MO) analysis. For M 2(η4-E4)2 (M = Al, Ga; E = P, As), the metal-ligand interactions are covalent, while for Al 2(η4-N4)2 the interactions between the Al atoms and the N42- ligands are ionic. According to the calculated dissociation energies for breaking metal-metal bonds, the Al-Al and Ga-Ga bonds are very strong indicating that these stable sandwich-like compounds Al2(η4-E4) 2 (E = N, P, As) and Ga2(η4-E 4)2 (E = P, As) may be synthesized in future experiments. The nitrogen-rich compounds Al2(η4-N4) 2 and Ga2(η2-N4)2 may be used as potential candidates of high energy density materials (HEDMs). Nucleus-independent chemical shifts (NICS) values reveal that the E 42- rings in the Al2(η4-E 4)2 (E = N, P, As) and Ga2(η4- E4)2 (E = P, As) species possess conflicting aromaticity (σ antiaromaticity and π aromaticity) and with the same ligands, the E42- ligands in Ga2(η4-E 4)2 have more aromaticity than those in Al 2(η4-E4)2.

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U2 - 10.1039/c1dt10508f

DO - 10.1039/c1dt10508f

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JO - Dalton Transactions

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The first binuclear sandwich-like complexes based on the aromatic tetraatomic species

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