Magic electron counts and bonding in tubular boranes

作者：Balakrishnarajan MM; Hoffmann R^*; Pancharatna PD; Jemmis ED

来源：Inorganic Chemistry, 2003, 42(15): 4650-4659.

DOI：10.1021/ic0262435

Ring stacking in some closo-borane dianions and the hypothetical capped borane nanotubes, predicted to be stable earlier, is analyzed in a perturbation theoretic way. A "staggered" building up of rings to form nanotubes is explored for four- and five-membered BnHn rings. Arguments are given for the stacking of B5H5 rings being energetically more favorable than the stacking of B4H4 rings. Elongated B-B distances in the central rings are predicted for some nanotubes, and the necessity to optimize ring-cap bonding is found to be responsible for this elongation. This effect reaches a maximum in B17H172- ; the insertion of additional rings will reduce this elongation. These closo-borane nanotubes obey Wade's n + 1 rule, but the traditional explanation based on a partitioning into radial/tangential molecular orbitals is wanting.

• 出版日期2003-7-28