Influence of N - and P -substituents in N -aryl-phosphinoglycine ligands on the selectivity of Ni-catalysed ethylene oligomerization

• Published in: New journal of chemistry 2022-09, Vol.46 (36), p.17303-17312
• Main Authors: Kagileva, Alina A., Kagilev, Alexey A., Kantyukov, Artyom O., Gafurov, Zufar N., Sakhapov, Il’yas F., Bekmukhamedov, Giyjaz E., Khayarov, Khasan R., Zueva, Ekaterina M., Soficheva, Olga S., Yakhvarov, Dmitry G.
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Atomic properties; Chemical synthesis; Ethylene; Ligands; Molecular weight distribution; Nitrogen; Oligomerization; Quantum chemistry; Selectivity; Steric effects; Thermodynamics
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/D2NJ02578G

The synthesised N -(phenyl)-, N -(pyrazin-2-yl)-, N -(pyridin-3-yl)-, N -(2,5-dimethoxycarbonylphenyl)-, N -(2-methoxycarbonylphenyl)- and the newly obtained so far unknown N -(2-carboxylphenyl)- and N -(pyridin-4-yl)-α-diphenylphosphinoglycines, as well as N -(pyrazin-2-yl)- and N -(2-methoxycarbonylphenyl)-α-mesityl(phenyl)phosphinoglycines were tested as ligands in nickel-catalysed homogeneous ethylene oligomerization. The resulting catalytic systems showed diverse selectivities. Quantum-chemical calculations were performed to rationalize the influence of substituents at nitrogen and phosphorus atoms in N -aryl-phosphinoglycines (L) on the molecular weight distribution of α-olefin products. It was revealed that the difference in the catalytic performance of L/Ni systems is mainly due to the steric effects influencing the relative thermodynamic stability of various conformations of the catalyst as well as the thermodynamic and kinetic parameters of various competing catalytic transformations.