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- Title
Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX<sub>3</sub>PF<sub>2</sub> (X = F, Cl): A Computational Study.
- Authors
Nixon, John F.; Nyulászi, László; Szieberth, Dénes
- Abstract
ABSTRACT Detailed computational studies have been carried out to explain the unexpected differing reactions that occur between dimethylamine and the difluorophosphines, CX3PF2 (X = F, Cl). The reaction affords the thermodynamically controlled product chloroform in the case of X = Cl, whereas when X = F the analogous reaction pathway leading to fluoroform is hindered by a substantial reaction barrier in the gas phase, where the reaction should take place due to the volatility of the reactant. While the gas-phase reaction energy gap is somewhat reduced when X = Cl, due to the stability of the migrating CCl3− moiety, the still substantial barrier does not account for the chloroform formation. Polarizable continuum model (PCM) calculations indicate a reduction of the barrier, facilitating the liquid-phase reaction. The alternative gas-phase reaction path, resulting in the aminolysis of a P-F bond is reversible and is shifted toward the product by capturing HF as the dimethylamino salt of the [CF3PF4H]− anion.
- Subjects
AMINES; SUBSTITUTION reactions; TRICHLOROMETHYL group; FLUOROPHOSPHINE; CHEMICAL reactions
- Publication
Heteroatom Chemistry, 2015, Vol 26, Issue 4, p307
- ISSN
1042-7163
- Publication type
Article
- DOI
10.1002/hc.21261