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Issue 26, 2011
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The first binuclear sandwich-like complexes based on the aromatic tetraatomic species

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Abstract

The first binuclear sandwich-like complexes based on the aromatic tetraatomic species with formula M24-E4)2 (M = Al, Ga; E = N, P, As) have been studied by density functional theory (DFT). The stable conformer for each M24-E4)2 is the staggered one with D4d symmetry except for Ga22-N4)2 with C2v symmetry. Natural bonding orbital (NBO) analysis indicates that the metal–metal bonds of Al24-E4)2 (E = N, P, As) and Ga24-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 M24-E4)2 (M = Al, Ga; E = P, As), the metal–ligand interactions are covalent, while for Al24-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 Al24-E4)2 (E = N, P, As) and Ga24-E4)2 (E = P, As) may be synthesized in future experiments. The nitrogen-rich compounds Al24-N4)2 and Ga22-N4)2 may be used as potential candidates of high energy density materials (HEDMs). Nucleus-independent chemical shifts (NICS) values reveal that the E42 rings in the Al24-E4)2 (E = N, P, As) and Ga24-E4)2 (E = P, As) species possess conflicting aromaticity (σ antiaromaticity and π aromaticity) and with the same ligands, the E42 ligands in Ga24-E4)2 have more aromaticity than those in Al24-E4)2.

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

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Publication details

The article was received on 25 Mar 2011, accepted on 15 Apr 2011 and first published on 02 Jun 2011


Article type: Paper
DOI: 10.1039/C1DT10508F
Dalton Trans., 2011,40, 6922-6928

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

    C. Wang, N. Li, X. Zhang, L. Ji and Q. Li, Dalton Trans., 2011, 40, 6922
    DOI: 10.1039/C1DT10508F

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