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.
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.
Wilhelm-Ostwald-Institut ür Physikalische und Theoretische Chemie, Universität Leipzig, Germany. didio@uni-leipzig.de
Philipp J
PJ
di Dio
Marc
M
Brüssel
Kilian
K
Muñiz
Rupashree Shyama
RS
Ray
Stefan
S
Zahn
Barbara
B
Kirchner
D002219:Carbamates / Q000138:chemical synthesis* / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D008697:Methane / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D011789:Quantum Theory
D002219:Carbamates; D009942:Organometallic Compounds; D002245:Carbon Dioxide; D010165:Palladium; D009584:Nitrogen; D008697:Methane; D010100:Oxygen