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Issue 46, 2011
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All-metal aromatic clustersM42 (M = B, Al, and Ga). Are π-electrons distortive or not?

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The π-electrons in benzene, the quintessential aromatic molecule, were previously shown to be distortive, i.e., they prefer localized double bonds alternating with single bonds. It is the σ-electrons that force the double bonds to delocalize, leading to a regular, D6h geometry. Herein, we computationally investigate the double-bond localizing or delocalizing propensities of σ- and π-electrons in the archetypal all-metal aromatic cluster Al42 and its second- and fourth-period analogs B42 and Ga42, using Kohn–Sham molecular orbital (MO) theory at BP86/TZ2P in combination with quantitative bond energy decomposition analyses (EDA). We compare the three all-metal aromatic clusters with the structurally related organic species C4H42+, C4H4, and C4H42. Our analyses reveal that the π-electrons in the group-13 M42 molecules have a weak preference for localizing the double bonds. Instead, the σ-electrons enforce the regular D4h equilibrium geometry with delocalized double bonds.

Graphical abstract: All-metal aromatic clusters M42− (M = B, Al, and Ga). Are π-electrons distortive or not?

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The article was received on 29 Aug 2011, accepted on 29 Sep 2011 and first published on 20 Oct 2011

Article type: Paper
DOI: 10.1039/C1CP22759A
Phys. Chem. Chem. Phys., 2011,13, 20673-20681

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    All-metal aromatic clusters M42 (M = B, Al, and Ga). Are π-electrons distortive or not?

    J. Poater, F. Feixas, F. M. Bickelhaupt and M. Solà, Phys. Chem. Chem. Phys., 2011, 13, 20673
    DOI: 10.1039/C1CP22759A

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