caa a22 4500 60551111X CHVBK 20210128100649.0 cr unu---uuuuu 210128e20150901xx s 000 0 eng 10.1007/s00894-015-2770-6 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2770-6 The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective [Elektronische Daten] [Oleksandra Trofymchuk, Daniela Ortega, Soledad Gutiérrez-Oliva, René Rojas, Alejandro Toro-Labbé] 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 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. Springer-Verlag Berlin Heidelberg, 2015 Chemical reactivity nationallicence Reactivity of catalysts nationallicence Methallyl Nickel catalysts nationallicence Conceptual DFT nationallicence Electronic chemical potential, hardness and electrophilicity nationallicence Trofymchuk Oleksandra Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut Ortega Daniela Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut Gutiérrez-Oliva Soledad Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut Rojas René Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut Toro-Labbé Alejandro Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/9(2015-09-01), 1-10 1610-2940 21:9<1 2015 21 894 https://doi.org/10.1007/s00894-015-2770-6 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2770-6 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Trofymchuk Oleksandra Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut NATIONALLICENCE 700 1- Ortega Daniela Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut NATIONALLICENCE 700 1- Gutiérrez-Oliva Soledad Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut NATIONALLICENCE 700 1- Rojas René Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut NATIONALLICENCE 700 1- Toro-Labbé Alejandro Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/9(2015-09-01), 1-10 1610-2940 21:9<1 2015 21 894