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- Title
Full kinetics investigation of the formation reaction of phosphonate esters in the gas-phase: a theoretical study.
- Authors
Kazemian, Mohammad; Habibi-Khorassani, Sayyed; Maghsoodlu, Malek; Ebrahimi, Ali
- Abstract
In the present work, the proposed multiple-mechanisms have been investigated theoretically for the reaction between triphenyl phosphite and dimethyl acetylenedicarboxylate in the presence of N-H acid such as aniline for generation of phosphonate esters using ab initio molecular orbital theory in gas phase. The profile of the potential energy surface was constructed at the HF/6-311G(d,p) level of theory. The kinetics of the gas phase reaction was studied by evaluating the reaction path of various mechanisms. Between 12 speculative proposed mechanisms {step, step (with four possibilities), step (with three possibilities), and step} only the third speculative mechanism was recognized as a desirable mechanism. Theoretical kinetics data involving k and E, activation (Δ G, Δ S and Δ H), and thermodynamic parameters (Δ G°, Δ S° and Δ H) were calculated for each step of the various mechanisms. Step of the desirable mechanism was identified as the rate determining step. Comparison of the theoretical desirable mechanism with the rate law that has been previously obtained by UV spectrophotometry experiments indicated that the results are in good agreement.
- Subjects
PHOSPHONATES; ESTERS; TRIPHENYL phosphite; MOLECULAR orbitals; CHEMICAL kinetics; ULTRAVIOLET spectrophotometry; GAS phase reactions
- Publication
Journal of Molecular Modeling, 2014, Vol 20, Issue 4, p1
- ISSN
1610-2940
- Publication type
Article
- DOI
10.1007/s00894-014-2103-1