On preference of insertion mechanism in the ethylene polymerization catalyzed by half-titanocene complexes with aryloxy ligands: Static and dynamic theoretical studies

Monika Srebro; Lukasz Piekos; Artur Michalak; Tae-Jin Kim; Sang Ook Kang; Minserk Cheong; Myung-Ahn Ok

Macromolecular Research, Vol.18, No.10, 960-966, October, 2010

DOI10.1007/s13233-010-1012-0 Export Citation

On preference of insertion mechanism in the ethylene polymerization catalyzed by half-titanocene complexes with aryloxy ligands: Static and dynamic theoretical studies

Monika Srebro, Lukasz Piekos, Artur Michalak^†, Tae-Jin Kim¹, Sang Ook Kang¹, Minserk Cheong², and Myung-Ahn Ok³

Department of Theoretical Chemistry, Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060, Cracow, Poland
¹Department of Materials Chemistry, Sejong Campus, Korea University, Chung-nam, 339-700, Korea
²Department of Chemistry and Research Institute for Basic Sciences, Kyung Hee University, Seoul, 130-701, Korea
³SK Corporation R&D Center, Daejeon, 305-712, Korea

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The Ziegler-Rauk bond-energy decomposition analysis was performed for the frontside (FS) and backside (BS) transition states of ethylene insertion in the processes catalyzed by half-titanocenes with phenoxy ligands to rationalize the origin of the energetic preference of the backside insertion observed for the complexes with monosubstituted phenoxide(Type 4 catalysts). The final preference of the backside or frontside transition state comes as a balance between the electronic preference of the former, and the steric preference of the latter. The unique energetic preference of the backside insertion observed for Type 4 catalysts appears to be a result of reduced steric crowding. The openness near the metal center and conformational flexibility leads to enhanced catalytic activity of those systems. In addition, Car-Parinello molecular dynamic simulations were carried out to examine the influence of entropic effects on the preference of the insertion mechanism. For Type 4 catalysts, the spontaneous frontside insertion was observed. Therefore, at the free-energy level, frontside insertion becomes viable due to entropic destabilization of the backside transition state.

Keywords:ethylene polymerization;half-titanocenes;backside/frontside insertion preference;density functional calculations;molecular dynamic simulations

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[6] Sita LR, Babcock R, Organometallics, 17, 5228 (1998)

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[8] Manz TA, Phomphrai K, Medvedev G, Krishnamurthy BB, Sharma S, Haq J, Novstrup KA, Thomson KT, Delgass WN, Caruthers JM, Abu-Omar MM, J. Am. Chem. Soc., 129(13), 3776 (2007)

[9] Chen YX, Marks TJ, Organometallics, 16, 3649 (1997)

[10] Stevens JC, Stud. Surf. Sci. Catal., 89, 277 (1994)

[11] Stevens JC, Stud. Surf. Sci. Catal., 101, 11 (1996)

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[13] Hanaoka H, Hino T, Nabika M, Kohno T, Yanagi K, Oda Y, Imai A, Mashima K, J. Organomet. Chem., 692, 4717 (2007)

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[36] te Velde G, Baerends EJ, J. Comput. Phys., 99, 84 (1992)

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[38] CPMD, Copyright IBM Corp 1990.2006, Copyright MPI fur Festkorperforschung Stuttgart 1997-2001.

[39] Hartwigsen C, Goedecker S, Hutter JK, Phys. Rev. B, 58, 3641 (1998)