Abstract
Structure and stability of BH4CN, a possible intermediate in the BH3CN aqueous hydrolysis, were analyzed by ab initio molecular orbital calculations. With an endothermic association energy of 1.2 kcal mol-1 at the coupled cluster method with single, double, and triple excitations- (CCSD(T))/augmented correlation-consistent polarized valence-triple-ζ (aug- cc-pVTZ)//MP2/6-311++G(d,p) level, BH4CN is 1.7 kcal mol-1 less stable toward H2 loss than its BH5 analog. Due to its increased acidity conferred by the CN electron withdrawing group, BH4CN is stabilized by 6.4 kcal mol- 1 upon H2O complexation compared to only 2.9 kcal mol-1 in the case of BH5, which may be partly responsible for the enhanced stability toward acidic conditions of BH3CN- relative to BH-4. (C) 2000 Elsevier Science B.V.
Original language | English |
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Pages (from-to) | 95-101 |
Number of pages | 7 |
Journal | Journal of Molecular Structure: THEOCHEM |
Volume | 505 |
Issue number | 1-3 |
DOIs | |
State | Published - Jun 26 2000 |
Externally published | Yes |
Keywords
- Ab initio calculations
- Borohydrides
- Cyanoborohydrides