Get 20M+ Full-Text Papers For Less Than $1.50/day. Start a 14-Day Trial for You or Your Team.

Learn More →

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX 3 PF 2 (X = F, Cl): A Computational Study

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl... 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. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Heteroatom Chemistry Wiley

Remarkable Differences in Amine Substitution Reactions of Trichloromethyl and Trifluoromethyl Difluorophosphines, CX 3 PF 2 (X = F, Cl): A Computational Study

Loading next page...
 
/lp/wiley/remarkable-differences-in-amine-substitution-reactions-of-v8kFEH0oZ6

References (14)

Publisher
Wiley
Copyright
Copyright © 2015 Wiley Periodicals, Inc.
ISSN
1042-7163
eISSN
1098-1071
DOI
10.1002/hc.21261
Publisher site
See Article on Publisher Site

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.

Journal

Heteroatom ChemistryWiley

Published: Jul 1, 2015

There are no references for this article.