The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective

• Published in: Journal of molecular modeling 2015-09, Vol.21 (9), p.227-227, Article 227
• Main Authors: Trofymchuk, Oleksandra S., Ortega, Daniela E., Gutiérrez-Oliva, Soledad, Rojas, René S., Toro-Labbé, Alejandro
• Format: Article
• Language: English
• Subjects: Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Molecular Medicine; Original Paper; Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-015-2770-6

In this work, global and local descriptors of chemical reactivity and selectivity are used to explain the differences in reactivities toward ethylene of methallyl nickel complexes and their B(C 6 F 5 ) 3 and BF 3 adducts. DFT calculations were used to explain why nickel complexes alone are inactive in ethylene polymerization while their boron adducts can activate it. It is shown that chemical potential, hardness, electrophilicity and molecular electrostatic potential surfaces describe fairly well the reactivity and selectivity of these organometallic systems toward ethylene. Experimental data indicates that addition of a borane molecule to nickel complexes changes dramatically their reactivity—behavior that is confirmed computationally. Our results show that bare complexes are unable to activate ethylene—a Lewis base—because they also behave as Lewis bases. The addition of the co-catalyst—a Lewis acid—turns the adducts into Lewis acids, making them active towards ethylene.