Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes with formate salts: a computational studyElectronic supplementary information (ESI) available: Additional discussions of computational results; Cartesian coordinates and energies of the optimized structures. See DOI: 10.1039/c8cy00405f

Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and... The origin of ligand effects on pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes was investigated using density functional theory (DFT) calculations. The computations reveal that the CO2 insertion into allylpalladium and benzylpalladium intermediates is the rate-determining step for both allene and alkene substrates. Distortion/interaction analysis indicates that CO2 insertion into the benzylpalladium intermediate via a 3-membered transition state has larger distortion energy than that of CO2 reacting with the allylpalladium intermediate through a 6-membered transition state. The linear relationships between the distortion energy and the activation energy are applicable for a series of PGeP-pincer ligands with different P-bound R substituents. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Catalysis Science & Technology Royal Society of Chemistry

Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes with formate salts: a computational studyElectronic supplementary information (ESI) available: Additional discussions of computational results; Cartesian coordinates and energies of the optimized structures. See DOI: 10.1039/c8cy00405f

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Publisher
The Royal Society of Chemistry
Copyright
This journal is © The Royal Society of Chemistry
ISSN
2044-4753
eISSN
2044-4761
D.O.I.
10.1039/c8cy00405f
Publisher site
See Article on Publisher Site

Abstract

The origin of ligand effects on pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes was investigated using density functional theory (DFT) calculations. The computations reveal that the CO2 insertion into allylpalladium and benzylpalladium intermediates is the rate-determining step for both allene and alkene substrates. Distortion/interaction analysis indicates that CO2 insertion into the benzylpalladium intermediate via a 3-membered transition state has larger distortion energy than that of CO2 reacting with the allylpalladium intermediate through a 6-membered transition state. The linear relationships between the distortion energy and the activation energy are applicable for a series of PGeP-pincer ligands with different P-bound R substituents.

Journal

Catalysis Science & TechnologyRoyal Society of Chemistry

Published: May 15, 2018

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