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Theoretical study of hydrogenation of the doubly aromatic B −7 cluster

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Abstract

We have studied the influence of hydrogenation on the relative stability of the low-lying isomers of the anionic B −7 cluster, computationally. It is known that the pure-boron B −7 cluster has a doubly (σ- and π-) aromatic C6v (3A1) quasi-planar wheel-type triplet global minimum (structure 1), a low-lying σ-aromatic and π-antiaromatic quasi-planar singlet C2v (1A1) isomer 2 (0.7 kcal mol−1 above the global minimum), and a planar doubly (σ- and π-) antiaromatic C2v (1A1) isomer 3 (7.8 kcal mol−1 above the global minimum). However, upon hydrogenation, an inversion in the stability of the species occurs. The planar B7H −2 (C2v, 1A1) isomer 4, originated from the addition of two hydrogen atoms to the doubly antiaromatic B −7 isomer 3, becomes the global minimum structure. The second most stable B7H −2 isomer 5, originated from the quasi-planar triplet wheel isomer 1 of B −7 , was found to be 27 kcal mol−1 higher in energy. The inversion in stability occurs due to the loss of the doubly aromatic character in the wheel-type global minimum isomer (C6v, 3A1) of B −7 upon H2−addition. In contrast, the planar isomer of B −7 (C2v, 1A1) gains aromatic character upon addition of two hydrogen atoms, which makes it more stable.

The B7H2-global minimum structure and its σ-aromatic and π-antiaromatic MOs

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Acknowledgments

This work was supported partially by the donors of The Petroleum Research Fund (ACS-PRF# 38242-AC6), administered by the American Chemical Society, partially by the National Science Foundation (CHE-0404937), and partially by the Summer Research Institute at the Pacific Northwest National Laboratory operated by Battelle, Richland, Washington, USA.

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  1. Department of Chemistry and Biochemistry, Utah State University, 0300 Old Main Hill, Logan, UT, 84322-0300, USA

    Anastassia N. Alexandrova, Eldon Koyle & Alexander I. Boldyrev

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  1. Anastassia N. Alexandrova
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  2. Eldon Koyle
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  3. Alexander I. Boldyrev
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Correspondence to Alexander I. Boldyrev.

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Dedicated to Professor Dr. Paul von Ragué Schleyer on the occasion of his 75th birthday.

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Alexandrova, A.N., Koyle, E. & Boldyrev, A.I. Theoretical study of hydrogenation of the doubly aromatic B −7 cluster. J Mol Model 12, 569–576 (2006). https://doi.org/10.1007/s00894-005-0035-5

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