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  • Title: A short yet very weak dative bond: structure, bonding, and energetic properties of N(2)-BH(3).
    Author: Smith EL, Sadowsky D, Phillips JA, Cramer CJ, Giesen DJ.
    Journal: J Phys Chem A; 2010 Feb 25; 114(7):2628-36. PubMed ID: 20121205.
    Abstract:
    The structure, bonding, and energetic properties of the N(2)-BH(3) complex are reported as characterized by density functional theory (DFT) and post-Hartree-Fock (HF) calculations. The equilibrium structure of the complex exhibits a short B-N distance near 1.6 A, comparable to that of a strong acid-base complex like H(3)N-BH(3). However, the binding energy is only 5.7 kcal/mol at the CCSD(T)/6-311+G(2df,2dp) level of theory, which is reminiscent of a weak, nonbonded complex. Natural bond orbital (NBO) and atoms in molecules (AIM) analyses of the electron density from both DFT and post-HF calculations do indicate that the extent of charge transfer and covalent character in the B-N dative bond is only somewhat less than in comparable systems with fairly large binding energies (e.g., H(3)N-BH(3) and OC-BH(3)). Energy decomposition analysis indicates key differences between the N(2), CO, and NH(3) complexes, primarily associated with the natures of the lone pairs involved (sp vs sp(3)) and the donor/acceptor characteristics of the relevant occupied and virtual orbitals, both sigma and pi. Also, CCSD/6-311+G(2df,2dp) calculations indicate that the B-N distance potential is rather anharmonic and exhibits a flat, shelf-like region ranging from 2.1 to 2.5 A that lies about 1.5 kcal/mol above the minimum at 1.67 A. However, this region is more sloped and lies about 2.5 kcal/mol above the equilibrium region according to the CCSD(T)/6-311+G(2df,2dp)//CCSD/6-311+G(2df,2dp) potential. A 1D analysis of the vibrational motion along the B-N stretching coordinate in the CCSD/6-311+G(2df,2dp) potential indicates that the average B-N distance in the ground vibrational state is 1.71 A, about 0.04 A longer than the equilibrium distance. Furthermore, the vibrationally averaged distance obtained via an analysis of the CCSD(T)/6-311+G(2df,2dp)//CCSD/6-311+G(2df,2dp) potential was found to be 0.03 A longer than the CCSD(T)/6-311+G(2df,2dp) minimum.
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