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- W2025831483 endingPage "7941" @default.
- W2025831483 startingPage "7926" @default.
- W2025831483 abstract "Poly(phenylacetylene) (PPA) has versatile electrical and optical properties due to its intriguing π-conjugated backbone, configuration, stereoregularity, and helical conformation. Detailed DFT, ONIOM, and ONIOM-MD studies are presented to understand the mechanisms of Rh-catalyzed polymerization of phenylacetylene and the factors that control its regioselectivity and stereochemistry. The polymerization proceeds via the RhI insertion mechanism (ΔH⧧ ≈ 9 kcal/mol), although all the RhI, RhIII, and Rh-carbene types of active species are thermodynamically and kinetically plausible in solution; the RhIII insertion and the Rh-carbene metathesis mechanisms both have higher activation enthalpies (∼22 and ∼25 kcal/mol, respectively). Phenylacetylene prefers a 2,1-inserion, leading to head-to-tail regioselective PPA via a unique π-conjugative transition state. This π-conjugative characteristic specifically favors the 2,1-insertion due to the steric repulsion. Kinetic factors play a key role in the stereoregularity. The polymerization adopting a cis–transoidal conformation is the most favorable. The kinetic difference for the insertion originates in the conformational constraints of the parent propagation chain in the transition state. These fundamental guidelines should help advance the development of efficient and structurally tailorable PPA catalysts." @default.
- W2025831483 created "2016-06-24" @default.
- W2025831483 creator A5020600412 @default.
- W2025831483 creator A5022393729 @default.
- W2025831483 creator A5025649330 @default.
- W2025831483 creator A5068700347 @default.
- W2025831483 date "2011-05-02" @default.
- W2025831483 modified "2023-09-27" @default.
- W2025831483 title "Rh-Catalyzed Polymerization of Phenylacetylene: Theoretical Studies of the Reaction Mechanism, Regioselectivity, and Stereoregularity" @default.
- W2025831483 cites W1571264866 @default.
- W2025831483 cites W1964395161 @default.
- W2025831483 cites W1964837435 @default.
- W2025831483 cites W1965615749 @default.
- W2025831483 cites W1966240115 @default.
- W2025831483 cites W1968187713 @default.
- W2025831483 cites W1968344479 @default.
- W2025831483 cites W1968501697 @default.
- W2025831483 cites W1968760519 @default.
- W2025831483 cites W1969140552 @default.
- W2025831483 cites W1969472814 @default.
- W2025831483 cites W1969694854 @default.
- W2025831483 cites W1971153261 @default.
- W2025831483 cites W1971953363 @default.
- W2025831483 cites W1973727162 @default.
- W2025831483 cites W1975720382 @default.
- W2025831483 cites W1976960884 @default.
- W2025831483 cites W1976981881 @default.
- W2025831483 cites W1977086107 @default.
- W2025831483 cites W1977571723 @default.
- W2025831483 cites W1978036379 @default.
- W2025831483 cites W1984289264 @default.
- W2025831483 cites W1987026120 @default.
- W2025831483 cites W1987616597 @default.
- W2025831483 cites W1988786558 @default.
- W2025831483 cites W1988859674 @default.
- W2025831483 cites W1991607416 @default.
- W2025831483 cites W1992173555 @default.
- W2025831483 cites W1992686717 @default.
- W2025831483 cites W1993209440 @default.
- W2025831483 cites W1994093365 @default.
- W2025831483 cites W1994972108 @default.
- W2025831483 cites W1995350002 @default.
- W2025831483 cites W1998792404 @default.
- W2025831483 cites W1999332606 @default.
- W2025831483 cites W2001838359 @default.
- W2025831483 cites W2008750079 @default.
- W2025831483 cites W2008828355 @default.
- W2025831483 cites W2011215428 @default.
- W2025831483 cites W2011660593 @default.
- W2025831483 cites W2011917510 @default.
- W2025831483 cites W2012320554 @default.
- W2025831483 cites W2020088371 @default.
- W2025831483 cites W2020769082 @default.
- W2025831483 cites W2020985693 @default.
- W2025831483 cites W2021149057 @default.
- W2025831483 cites W2021214676 @default.
- W2025831483 cites W2021480093 @default.
- W2025831483 cites W2023099374 @default.
- W2025831483 cites W2023271753 @default.
- W2025831483 cites W2024694153 @default.
- W2025831483 cites W2026101712 @default.
- W2025831483 cites W2029246821 @default.
- W2025831483 cites W2030971064 @default.
- W2025831483 cites W2031518824 @default.
- W2025831483 cites W2031726130 @default.
- W2025831483 cites W2038533471 @default.
- W2025831483 cites W2039666220 @default.
- W2025831483 cites W2040527442 @default.
- W2025831483 cites W2042029879 @default.
- W2025831483 cites W2042263399 @default.
- W2025831483 cites W2043441287 @default.
- W2025831483 cites W2045658293 @default.
- W2025831483 cites W2046038973 @default.
- W2025831483 cites W2048217496 @default.
- W2025831483 cites W2048520227 @default.
- W2025831483 cites W2048856816 @default.
- W2025831483 cites W2050282085 @default.
- W2025831483 cites W2050949850 @default.
- W2025831483 cites W2056968862 @default.
- W2025831483 cites W2060036289 @default.
- W2025831483 cites W2060275680 @default.
- W2025831483 cites W2060702364 @default.
- W2025831483 cites W2068964866 @default.
- W2025831483 cites W2070084073 @default.
- W2025831483 cites W2070311378 @default.
- W2025831483 cites W2074451271 @default.
- W2025831483 cites W2075733276 @default.
- W2025831483 cites W2076658032 @default.
- W2025831483 cites W2077229900 @default.
- W2025831483 cites W2078261810 @default.
- W2025831483 cites W2080053067 @default.
- W2025831483 cites W2081992801 @default.
- W2025831483 cites W2082420144 @default.
- W2025831483 cites W2085779700 @default.
- W2025831483 cites W2087943725 @default.
- W2025831483 cites W2089759714 @default.
- W2025831483 cites W2093481402 @default.
- W2025831483 cites W2100174671 @default.