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• W2023692017 endingPage "16546" @default.
• W2023692017 startingPage "16533" @default.
• W2023692017 abstract "This contribution focuses on the catalytic properties of the organozirconium precatalyst Cp2Zr(CH3)2 chemisorbed on dehydroxylated gamma-alumina (Al2O3), as analyzed via density functional theory. The interactions of the catalytically active cationic Cp2ZrCH3+ adsorbate species are scrutinized at two possible model Al2O3 (110) surface sites, namely mu2-O and mu3-O, representing the principal reactive species on the alumina surface. It is found that zirconocenium coordination occurs via two different geometries (dioxo-bridged and oxo-bridged) at both the mu-O and mu2-O surface sites. This process is compared to that for forming the related homogeneous phase Cp2ZrCH3+H3CB(CeFs)3- ion pair structure. It is found that the interaction of the Cp2ZrCH3 adsorbate species with the Pr2-O sites is far stronger than that with the B3-O sites due to the greater unsaturation of the former. Furthermore, the interaction with the mu3-O sites is weaker than that in the parent homogeneous ion pair. The catalytic activity of the chemisorbed Cp2ZrCH3+ systems for ethylene polymerization is investigated at both mu2-O and mu3-O sites and compared with the analogous Cp2ZrCH3+H3CB(C6F5)3- -mediated process in solution. A Cossee enchainment mechanism proceeds via ethylene pi-complex formation and an alpha-agostic assisted transition state to yield gamma- and beta-agostic insertion products. The overall kinetics of enchainment are closely correlated with the energetics of pi-complex formation, and it is suggested that the differing kinetic behaviors of the surface-bound Cp2ZrR+ species on the various Al2O3 coordination sites and the analogous homogeneous species reflect differences in the olefin pi-complex stabilization energies. These computational results agree well with the experimental data which indicate that only fractions of the surface bound species are catalytically significant but that these are far more catalytically active than the homogeneous analogues." @default.
• W2023692017 created "2016-06-24" @default.
• W2023692017 creator A5000731301 @default.
• W2023692017 creator A5016296466 @default.
• W2023692017 creator A5044454837 @default.
• W2023692017 date "2008-11-14" @default.
• W2023692017 modified "2023-10-15" @default.
• W2023692017 title "Links Between Single-Site Heterogeneous and Homogeneous Catalysis. DFT Analysis of Pathways for Organozirconium Catalyst Chemisorptive Activation and Olefin Polymerization on γ-Alumina" @default.
• W2023692017 cites W1650728208 @default.
• W2023692017 cites W1965295403 @default.
• W2023692017 cites W1965752441 @default.
• W2023692017 cites W1966750682 @default.
• W2023692017 cites W1969386552 @default.
• W2023692017 cites W1971241275 @default.
• W2023692017 cites W1976711790 @default.
• W2023692017 cites W1977168693 @default.
• W2023692017 cites W1978875624 @default.
• W2023692017 cites W1979058149 @default.
• W2023692017 cites W1986632875 @default.
• W2023692017 cites W1991149034 @default.
• W2023692017 cites W1991542528 @default.
• W2023692017 cites W1993023761 @default.
• W2023692017 cites W1993610879 @default.
• W2023692017 cites W1994080636 @default.
• W2023692017 cites W1996455423 @default.
• W2023692017 cites W1999564735 @default.
• W2023692017 cites W2000343675 @default.
• W2023692017 cites W2000883516 @default.
• W2023692017 cites W2002064411 @default.
• W2023692017 cites W2002676693 @default.
• W2023692017 cites W2003162132 @default.
• W2023692017 cites W2004446721 @default.
• W2023692017 cites W2006792934 @default.
• W2023692017 cites W2007210502 @default.
• W2023692017 cites W2007767017 @default.
• W2023692017 cites W2010147612 @default.
• W2023692017 cites W2010363120 @default.
• W2023692017 cites W2011987956 @default.
• W2023692017 cites W2013872101 @default.
• W2023692017 cites W2014569369 @default.
• W2023692017 cites W2014659390 @default.
• W2023692017 cites W2015773551 @default.
• W2023692017 cites W2015876957 @default.
• W2023692017 cites W2017736005 @default.
• W2023692017 cites W2018455188 @default.
• W2023692017 cites W2020459210 @default.
• W2023692017 cites W2020642736 @default.
• W2023692017 cites W2022999656 @default.
• W2023692017 cites W2024299663 @default.
• W2023692017 cites W2028586947 @default.
• W2023692017 cites W2031775542 @default.
• W2023692017 cites W2034329598 @default.
• W2023692017 cites W2035377915 @default.
• W2023692017 cites W2035815155 @default.
• W2023692017 cites W2036109497 @default.
• W2023692017 cites W2040466840 @default.
• W2023692017 cites W2040722151 @default.
• W2023692017 cites W2042044087 @default.
• W2023692017 cites W2043390423 @default.
• W2023692017 cites W2044255068 @default.
• W2023692017 cites W2045490147 @default.
• W2023692017 cites W2051166993 @default.
• W2023692017 cites W2052814100 @default.
• W2023692017 cites W2053286705 @default.
• W2023692017 cites W2054664173 @default.
• W2023692017 cites W2055024553 @default.
• W2023692017 cites W2058506610 @default.
• W2023692017 cites W2058761984 @default.
• W2023692017 cites W2061566121 @default.
• W2023692017 cites W2065217844 @default.
• W2023692017 cites W2065573242 @default.
• W2023692017 cites W2067306308 @default.
• W2023692017 cites W2067666762 @default.
• W2023692017 cites W2068484608 @default.
• W2023692017 cites W2076085552 @default.
• W2023692017 cites W2076736831 @default.
• W2023692017 cites W2078561860 @default.
• W2023692017 cites W2080251051 @default.
• W2023692017 cites W2083924613 @default.
• W2023692017 cites W2090655790 @default.
• W2023692017 cites W2091943837 @default.
• W2023692017 cites W2092244272 @default.
• W2023692017 cites W2093707628 @default.
• W2023692017 cites W2125979718 @default.
• W2023692017 cites W2135799094 @default.
• W2023692017 cites W2138533209 @default.
• W2023692017 cites W2139952730 @default.
• W2023692017 cites W2145493485 @default.
• W2023692017 cites W2146227273 @default.
• W2023692017 cites W2148152686 @default.
• W2023692017 cites W2148599378 @default.
• W2023692017 cites W2156603730 @default.
• W2023692017 cites W2157871632 @default.
• W2023692017 cites W264384344 @default.
• W2023692017 cites W2808501733 @default.
• W2023692017 cites W2949934452 @default.
• W2023692017 cites W4211164182 @default.
• W2023692017 cites W4212894238 @default.

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