Pd-N to Pd-O rearrangement for a carbamate synthesis from carbon dioxide and methane: a density functional and ab initio molecular dynamics metadynamics study

Angew Chem Int Ed Engl. 2011 Sep 5;50(37):A40-5.

Abstract

We investigated the key step of Pd-N to Pd-O rearrangement from a model catalytic cycle for the activation of carbon dioxide and methane with static quantum chemical calculations and metadynamics simulation. Our calculations show that different bottlenecks appear in the catalytic cycle but that the investigated rearrangement of the Pd-N to Pd-O bounded complex has a barrier ΔG(#)/ΔF(#) of approximately 20 kJ mol⁻¹ and is therefore accessible at ambient reaction conditions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbamates / chemical synthesis*
  • Carbamates / chemistry
  • Carbon Dioxide / chemistry*
  • Catalysis
  • Methane / chemistry*
  • Molecular Dynamics Simulation*
  • Molecular Structure
  • Nitrogen / chemistry
  • Organometallic Compounds / chemistry*
  • Oxygen / chemistry
  • Palladium / chemistry
  • Quantum Theory*

Substances

  • Carbamates
  • Organometallic Compounds
  • Carbon Dioxide
  • Palladium
  • Nitrogen
  • Methane
  • Oxygen