Comparative G2(MP2) Molecular Orbital Study of B3H7XH3 and H3BXH3 Donor−Acceptor Complexes (X = N, P, and As)
| Autor: | C. Serrar, A. Ouassas, A. Es-sofi, Abderrahim Boutalib, Ignacio Nebot-Gil, Abdellah Jarid, Francisco Tomás |
|---|---|
| Rok vydání: | 2002 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 106:9065-9070 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/jp020981x |
| Popis: | B3H7XH3 and H3BXH3 (X = N, P, and As) have been studied as donor−acceptor complex type at the G2(MP2) level of theory. Both single- and double-bridged structures of B3H7 Lewis acid are taken into account. Although the double-bridged structure is energetically favored in the isolated state, the coordination prefers the single-bridged one. The monoborane adducts adopt the staggered arrangement with C3v symmetry. The energetic analysis by natural bond orbital theory shows that the decrease of hyperconjugative contribution upon complexation in the B3H7 moiety has, as consequence, a loss of symmetry for B3H7XH3 (X= P and As) complexes. In the two series, the coordination is the result of two opposing interactions. The first one is stabilizing, developed between a‘ symmetry fragment molecular orbitals, and is mainly of 3MO-4e nature. The second one is destabilizing and developed between occupied molecular orbitals (2MO-4e) of donor and acceptor fragments having a‘‘ symmetry. Furthermore, in the case of BH3 comp... |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|