Speciation of ZnMe<inf>2</inf>, ZnMeCl, and ZnCl<inf>2</inf> in Tetrahydrofuran (THF), and Its Influence on Mechanism Calculations of Catalytic Processes

Juan Del Pozo, María Pérez-Iglesias, Rosana Álvarez, Agustí Lledós, Juan A. Casares, Pablo Espinet

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Abstract

© 2017 American Chemical Society. This paper examines the speciation of ZnMe2, ZnMeCl, and ZnCl2 in tetrahydrofuran (THF) solution, and provides experimental (infrared (IR) and calorimetric experiments) and density functional theory (DFT) data to conclude that the species in THF solution are, beyond a doubt, ZnMe2(THF)2, ZnMeCl(THF)2, and ZnCl2(THF)2. Consequently, coordinated THF should be used in DFT mechanistic calculations (e.g., Negishi reactions in THF). Naked or single THF coordinated molecules are virtually nonexistent in THF solutions. A cluster-continuum model for the solvent is recommended to obtain a more-correct representation. The presence or absence of THF produces a marked effect on the thermodynamics of the Negishi catalysis and a lesser effect on the kinetics of the transmetalation.
Original languageEnglish
Pages (from-to)3575-3583
JournalACS Catalysis
Volume7
Issue number5
DOIs
Publication statusPublished - 5 May 2017

Keywords

  • calorimetry
  • cluster continuum model
  • DFT and experimental
  • Negishi
  • THF solutions
  • transmetalation
  • ZnX speciation 2

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