The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective
Keywords: chemical reactivity, conceptual dft, Reactivity of catalysts, Methallyl Nickel catalysts, Electronic chemical potential, hardness and electrophilicity
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(C6F5)3 and BF3 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 de- scribe 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 con- firmed 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.
|Título según WOS:||The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective|
|Título según SCOPUS:||The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective|
|Título de la Revista:||Journal of Molecular Modeling|
|Fecha de publicación:||2015|
|Página de inicio:||1|