Electron flow in reaction mechanisms - Revealed from first principles

Gerald Knizia, Johannes E M N Klein

Research output: Contribution to journalArticle

107 Scopus citations

Abstract

The "curly arrow" of Robinson and Ingold is the primary tool for describing and rationalizing reaction mechanisms. Despite this approach's ubiquity and stellar success, its physical basis has never been clarified and a direct connection to quantum chemistry has never been found. Here we report that the bond rearrangements expressed by curly arrows can be directly observed in ab initio computations, as transformations of intrinsic bond orbitals (IBOs) along the reaction coordinate. Our results clarify that curly arrows are rooted in physical reality - a notion which has been challenged before - and show how quantum chemistry can directly establish reaction mechanisms in intuitive terms and unprecedented detail.

Original languageEnglish (US)
Pages (from-to)5518-5522
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number18
DOIs
StatePublished - Apr 27 2015

Keywords

  • ab initio calculations
  • bond theory
  • quantum chemistry
  • reaction mechanisms

PubMed: MeSH publication types

  • Journal Article

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