Understanding the [2n+2n] reaction mechanism between a carbenoid intermediate and CO2

Luis R. Domingo, Mar Ríos-Gutiérrez, Patricia Pérez, Eduardo Chamorro

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The mechanism of the cycloaddition reaction of CO2 with a nucleophilic carbenoid intermediate has been theoretically studied by using the bonding evolution theory (BET) at the B3LYP/6- 31G(d) level of theory. BET combines topological analysis of the electron localisation function and catastrophe theory along a reaction path. This cycloaddition reaction is characterised by 16 structural stability domains, associated to the following sequence of catastrophes: C8H9NO4 + CO2: 16- CFCFFCFFCC[FF]FFCC-0: C9H9NO6. Formation of the two new C-C and C-O single bonds evolves after the transition state structure is reached. The high nucleophilic character and the electronic structure of carbenoid intermediate together with the specific approaching mode of the CO2 molecule enable in fact the first C- C single bond formation after a very low activation enthalpy, 2.2 kcal/mol, without any external electrophilic activation. The subsequent ring closure via formation of the C - O single bond occurs at the end of the reaction. We propose thereafter a rationalisation of such a polar reaction process in terms of a [2n+2n] cycloaddition reaction following a nonconcerted two-stage one-step mechanism, in contrast to the simplified picture of rationalisation traditionally based on molecular orbitals.

Original languageEnglish
Pages (from-to)1374-1391
Number of pages18
JournalMolecular Physics
Volume114
Issue number7-8
DOIs
Publication statusPublished - 1 Feb 2016

Keywords

  • 1,3-dipolar cycloaddition
  • Bonding evolution theory (BET)
  • Catastrophe theory
  • Electron localization function (ELF)
  • Two-stage one-step mechanisms

ASJC Scopus subject areas

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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