Origin of ligand effects on reactivities of pincer-Pd catalyzed hydrocarboxylation of allenes and alkenes with formate salts: a computational study. Issue 11 (15th May 2018)

• Record Type: Journal Article
• Authors: Lv, Xiangying; Huang, Fang; Wu, Yan-Bo; Lu, Gang
• Is Part Of: Catalysis science & technology. Volume 8:Issue 11(2018)
• Page Start: 2835
• Page End: 2840
• Publication Date: 2018-05-15
• Subjects: Catalysis -- Periodicals; 541.395
• DOI: 10.1039/c8cy00405f
• Languages: English
• ISSNs: 2044-4753

Abstract

Abstract : Distortion induced by R substituents on PGeP -pincer ligands is the key factor affecting the reactivity of CO2 insertion into allylpalladium and benzylpalladium intermediates. 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.