4.8 Article

Two components in a molecule:: Highly efficient and thermally robust catalytic system for CO2/Epoxide copolymerization

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 129, Issue 26, Pages 8082-+

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ja071290n

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Salicylaldehyde compound containing an ammonium salt unit, [2-(HO)-3-tBu-5-{Bu3N+(CH2)(3)Si(Me-2)}C6H2C(O)H][BF4-], is prepared from which a Salen-type ligand and its cobalt(III) complex, (Salen-1)CoX (1: Salen-1 = [trans-N,N'-bis(3-tBu-5-(Bu3N+(CH2)(3)Si(Me-2)-salicylidene)-1,2-cyclohexanediamine)]X-2; X = 2,4-dinitrophenolate), is prepared. Complex 1 shows high activity for CO2/(propylene oxide) copolymerization even at a condition of high [propylene oxide]/[catalyst] ratio and high temperature up to 90 degrees C, at which conditions a typical binary system of [(Salen)CoX]/[PPNCl] does not yield any copolymer. A very high TOF (up to 3500 h(-1)) and TON (up to 14500) are achieved, which have never been attained with other catalytic systems. The high selectivity (> 84%) for the formation of copolymer over cyclic carbonate and the high molecular weight of the obtained polymers (M-n = 53000-95000) are the other merits of the catalyst.

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