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

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Abstract

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.

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Acknowledgments

Financial support from ICM N° 120082 (Nucleus Millenium CPC) and Fondo Nacional de Desarrollo Científico y Tecnológico(FONDECYT) projects Nos. 1100286, 1130072, l130077 and 1141098 are gratefully acknowledged. O. S. T. and D.E.O. acknowledge Vicerrectoría de Investigación of Pontificia Universidad Católica de Chile and La Comisión Nacional de Investigación Científica y Tecnológica (CONICYT) for PhD fellowships.

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Authors and Affiliations

  1. Nucleus Millennium Chemical Processes and Catalysis (CPC), Laboratorio de Química Inorgánica, Facultad de Química, Pontificia Universidad Católica de Chile, Casilla 306, Santiago-22, Chile

    Oleksandra S. Trofymchuk & René S. Rojas

  2. 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

    Daniela E. Ortega, Soledad Gutiérrez-Oliva & Alejandro Toro-Labbé

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  1. Oleksandra S. Trofymchuk
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  2. Daniela E. Ortega
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  3. Soledad Gutiérrez-Oliva
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  4. René S. Rojas
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  5. Alejandro Toro-Labbé
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Correspondence to Soledad Gutiérrez-Oliva, René S. Rojas or Alejandro Toro-Labbé.

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Trofymchuk, O.S., Ortega, D.E., Gutiérrez-Oliva, S. et al. The performance of methallyl nickel complexes and boron adducts in the catalytic activation of ethylene: a conceptual DFT perspective. J Mol Model 21, 227 (2015). https://doi.org/10.1007/s00894-015-2770-6

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