Matches in SemOpenAlex for { <https://semopenalex.org/work/W2059683257> ?p ?o ?g. }
- W2059683257 endingPage "5572" @default.
- W2059683257 startingPage "5565" @default.
- W2059683257 abstract "Combined gradient-corrected density functional theory and molecular mechanics (QM/MM) has been used to investigate the copolymerization of ethylene with the CH2CHX α-olefins, where X = −H, −Me, −CN, −COOMe, −OC(O)−Me, −Cl. The cationic N∧N−Pd(II) diimine complex and its modified neutral and anionic derivatives have been used as catalysts, where N∧N = −NR‘ ‘CR2CR3NR‘ ‘−, R‘ ‘ = aryl group, and R2, R3 = BH3-, H. The consecutive insertion steps of CH2CHX into the Pd−CH3 bond and of ethylene into the Pd−C(X)HCH2CH3 bond have been investigated. Focus has been put on the role of the X functional groups and the effect of the cationic, neutral, and anionic environments on the Pd(II)−diimine system. Calculations have been performed on the CH2CHX monomers, model catalysts, precursor π-complexes, and σ-complexes of the monomers, as well as the chelate and H-agostic insertion products. The transition state of the insertion reaction and the corresponding activation energy was determined for both investigated insertion steps. The results show that the X group has only a minor effect on the insertion of the CH2CHX monomers into the Pd−CH3 bond. On the other hand, the barrier for insertion of ethylene into the Pd−CHXR bond revealed an increase with the electron-withdrawing ability of X. We predict that the application of neutral and anionic catalysts leads to a preference for π-complexation over σ-complexation of the polar monomers. Unfortunately, for an anionic model system the barriers for the first and second insertion are significantly increased for ethylene, whereas the first insertion barrier for the polar monomers only is moderately increased. Thus, while anionic catalysts are highly tolerant toward polar monomers, they are nearly inactive toward ethylene insertion." @default.
- W2059683257 created "2016-06-24" @default.
- W2059683257 creator A5005444061 @default.
- W2059683257 creator A5011826172 @default.
- W2059683257 creator A5023582877 @default.
- W2059683257 creator A5038188328 @default.
- W2059683257 creator A5058003131 @default.
- W2059683257 creator A5066394814 @default.
- W2059683257 creator A5069425796 @default.
- W2059683257 date "2004-10-06" @default.
- W2059683257 modified "2023-09-23" @default.
- W2059683257 title "Polar Copolymerization by a Palladium−Diimine-Based Catalyst. Influence of the Catalyst Charge and Polar Substituent on Catalyst Poisoning and Polymerization Activity. A Density Functional Theory Study" @default.
- W2059683257 cites W1826233890 @default.
- W2059683257 cites W1963657741 @default.
- W2059683257 cites W1965378620 @default.
- W2059683257 cites W1967350455 @default.
- W2059683257 cites W1974618533 @default.
- W2059683257 cites W1985704326 @default.
- W2059683257 cites W1986119632 @default.
- W2059683257 cites W1987242438 @default.
- W2059683257 cites W1987675653 @default.
- W2059683257 cites W1989246295 @default.
- W2059683257 cites W1993736232 @default.
- W2059683257 cites W1993774897 @default.
- W2059683257 cites W1997455420 @default.
- W2059683257 cites W2002122522 @default.
- W2059683257 cites W2003162132 @default.
- W2059683257 cites W2004182290 @default.
- W2059683257 cites W2005421179 @default.
- W2059683257 cites W2007663400 @default.
- W2059683257 cites W2011421995 @default.
- W2059683257 cites W2012591289 @default.
- W2059683257 cites W2013464543 @default.
- W2059683257 cites W2014033694 @default.
- W2059683257 cites W2015707881 @default.
- W2059683257 cites W2016271477 @default.
- W2059683257 cites W2016521268 @default.
- W2059683257 cites W2016689740 @default.
- W2059683257 cites W2020537876 @default.
- W2059683257 cites W2023617553 @default.
- W2059683257 cites W2024954144 @default.
- W2059683257 cites W2028652707 @default.
- W2059683257 cites W2030687437 @default.
- W2059683257 cites W2030971064 @default.
- W2059683257 cites W2032108600 @default.
- W2059683257 cites W2034329598 @default.
- W2059683257 cites W2038675869 @default.
- W2059683257 cites W2041630224 @default.
- W2059683257 cites W2042313414 @default.
- W2059683257 cites W2048574139 @default.
- W2059683257 cites W2049543666 @default.
- W2059683257 cites W2051313301 @default.
- W2059683257 cites W2051508281 @default.
- W2059683257 cites W2055230539 @default.
- W2059683257 cites W2055613164 @default.
- W2059683257 cites W2056703412 @default.
- W2059683257 cites W2059022295 @default.
- W2059683257 cites W2060389497 @default.
- W2059683257 cites W2068054822 @default.
- W2059683257 cites W2073423625 @default.
- W2059683257 cites W2075471866 @default.
- W2059683257 cites W2076071234 @default.
- W2059683257 cites W2076595538 @default.
- W2059683257 cites W2081320329 @default.
- W2059683257 cites W2084058160 @default.
- W2059683257 cites W2085471688 @default.
- W2059683257 cites W2086487586 @default.
- W2059683257 cites W2086957099 @default.
- W2059683257 cites W2087719745 @default.
- W2059683257 cites W2099871009 @default.
- W2059683257 cites W2123195204 @default.
- W2059683257 cites W2141359017 @default.
- W2059683257 cites W2153900045 @default.
- W2059683257 cites W2161239029 @default.
- W2059683257 cites W2164128534 @default.
- W2059683257 cites W2950140863 @default.
- W2059683257 cites W3036723969 @default.
- W2059683257 cites W3107879085 @default.
- W2059683257 cites W350093642 @default.
- W2059683257 cites W4255389013 @default.
- W2059683257 doi "https://doi.org/10.1021/om049485g" @default.
- W2059683257 hasPublicationYear "2004" @default.
- W2059683257 type Work @default.
- W2059683257 sameAs 2059683257 @default.
- W2059683257 citedByCount "47" @default.
- W2059683257 countsByYear W20596832572012 @default.
- W2059683257 countsByYear W20596832572014 @default.
- W2059683257 countsByYear W20596832572015 @default.
- W2059683257 countsByYear W20596832572017 @default.
- W2059683257 countsByYear W20596832572018 @default.
- W2059683257 countsByYear W20596832572019 @default.
- W2059683257 countsByYear W20596832572020 @default.
- W2059683257 countsByYear W20596832572021 @default.
- W2059683257 countsByYear W20596832572022 @default.
- W2059683257 crossrefType "journal-article" @default.
- W2059683257 hasAuthorship W2059683257A5005444061 @default.
- W2059683257 hasAuthorship W2059683257A5011826172 @default.
- W2059683257 hasAuthorship W2059683257A5023582877 @default.