Catalyst-site-controlled coordination polymerization of polar vinyl monomers to highly syndiotactic polymers

Journal of the American Chemical Society
Yuetao ZhangEugene Y-X Chen

Abstract

This contribution reports a combined synthetic, kinetic, mechanistic, and theoretical/computational study of the recently discovered catalyst-site-controlled coordination polymerization of polar vinyl monomers [such as methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMAA)] into highly syndiotactic polymers. Among the 12 C(s)-ligated ansa-cyclopentadienyl (Cp)-R(2)E(C,Si)-fluorenyl (Flu) group 4 metallocene catalyst systems examined-which varied in metal center, anion structure, bridging atom and substituents, and ligand substitution pattern-cationic ansa-metallocene ester enolate catalyst 6(+)[B(C(6)F(5))(4)](-), derived from the activation of the precatalyst [Ph(2)C(Cp)(2,7-(t)Bu(2)-Flu)]Zr[OC(O(i)Pr)=CMe(2)](2) with [Ph(3)C][B(C(6)F(5))(4)], stood out as the best catalyst in all aspects of the MMA polymerization at room temperature, including the highest activity (1554 h(-1) TOF), efficiency (98% I*), syndiotacticity (94% rr), and control (predicted number-average molecular weight and 1.14 molecular weight distribution). Kinetic and mechanistic results are consistent with a catalyst-site-controlled, monometallic coordination-addition mechanism, involving fast intramolecular addition within the catalyst-monomer complex l...Continue Reading

References

Jan 9, 2003·Chemical Reviews·Vernon C Gibson, Stefan K Spitzmesser
Sep 8, 2004·Chemistry : a European Journal·Bing LianJean-François Carpentier
Jan 20, 2005·Journal of the American Chemical Society·Antonio Rodriguez-Delgado, Eugene Y-X Chen
Oct 13, 2006·Proceedings of the National Academy of Sciences of the United States of America·Tobin J Marks
Nov 16, 2006·Journal of the American Chemical Society·Logan E GarnerEugene Y-X Chen
May 8, 2007·Journal of the American Chemical Society·Garret M MiyakeEugene Y-X Chen
Feb 7, 2008·Journal of the American Chemical Society·Yalan Ning, Eugene Y-X Chen
Aug 1, 1988·Journal of the American Chemical Society·J A EwenJ D Ferrara

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Citations

May 10, 2017·Journal of the American Chemical Society·Yuxi HanYuetao Zhang
Sep 27, 2014·Chemical Society Reviews·Brenton A G HammerKlaus Müllen
Jul 16, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Garret M MiyakeEugene Y-X Chen
Jul 29, 2010·Chemistry : a European Journal·Yuetao ZhangEugene Y-X Chen
Mar 29, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Ravikumar R Gowda, Eugene Y-X Chen
Apr 8, 2011·Angewandte Chemie·David TürpKlaus Müllen
Jun 5, 2014·Organic Letters·Eleanor E MaciverStephen P Fletcher
Jun 12, 2013·The Journal of Physical Chemistry. B·Xinwei ChenJianwen Jiang
Jul 31, 2013·Journal of the American Chemical Society·Stephan SalzingerBernhard Rieger
Sep 29, 2020·Journal of the American Chemical Society·Travis P VarnerFrank A Leibfarth
Oct 22, 2021·Langmuir : the ACS Journal of Surfaces and Colloids·Beike CaiYongfeng Zhou

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