Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes with formate salts: a computational study
Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and...
Lv, Xiangying; Huang, Fang; Wu, Yan-Bo; Lu, Gang
2018-05-15 00:00:00
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.pngCatalysis Science & TechnologyRoyal Society of Chemistryhttp://www.deepdyve.com/lp/royal-society-of-chemistry/origin-of-ligand-effects-on-reactivities-of-pincer-pd-catalyzed-GVeg0wllwp
Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes with formate salts: a computational study
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 & Technology
– Royal Society of Chemistry
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