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Ebbe Nordlander. Portrait.

Ebbe Nordlander

Professor

Ebbe Nordlander. Portrait.

Cis- and trans molybdenum oxo complexes of a prochiral tetradentate aminophenolate ligand : Synthesis, characterization and oxotransfer activity

Author

  • Md Kamal Hossain
  • Anja Köhntopp
  • Matti Haukka
  • Michael G. Richmond
  • Ari Lehtonen
  • Ebbe Nordlander

Summary, in English

Reaction of [MoO2Cl2(dmso)2] with the tetradentate O2N2 donor ligand papy [H2papy = N-(2-hydroxybenzyl)-N-(2-picolyl)glycine] leads to formation of the dioxomolybdenum(VI) complex [MoO2(papy)] (1) as a mixture of cis and trans isomers. Recrystallization from methanol furnishes solid cis-1, whereas the use of a dichloromethane-hexane mixture allows for the isolation of the trans-1 isomer. Both isomers have been structurally characterized by X-ray crystallography and the energy difference between the isomeric pair has been investigated by electronic structure calculations. Optimization of two configurational isomers in the gas phase predicts the trans isomer to lie 2.5 kcal/mol lower in energy (ΔG) than the cis isomer, which is inconsistent with the solution NMR data in d3-MeCN that exhibit a Keq of ca. 3 at 298 K for the trans ⇌ cis equilibrium. The DFT-computed energy difference is significantly improved (Keq = 5.4) by the inclusion of the MeCN solvent using the polarization continuum model (PCM). Density functional calculations reveal that the isomerization proceeds via a Ray-Dutt twist mechanism with a barrier of 14.5 kcal/mol, which is in accordance with the 1H NMR spectral data and the rapid equilibration of these isomers in solution. The catalytic reactivity of [MoO2(papy)] in the epoxidation of cis-cyclooctene is described, as well as its ability to effect oxo transfer from DMSO to PPh3.

Department/s

  • Chemical Physics

Publishing year

2020-03-01

Language

English

Publication/Series

Polyhedron

Volume

178

Document type

Journal article

Publisher

Elsevier

Topic

  • Theoretical Chemistry (including Computational Chemistry)

Keywords

  • Computational modelling
  • Epoxidation
  • Oxo Atom Transfer
  • Tripodal ligand
  • Variable temperature NMR

Status

Published

ISBN/ISSN/Other

  • ISSN: 0277-5387