Kinetic Studies of Copolymerization of Cyclohexene Oxide with CO2 by a Diamino-bis(phenolate) Chromium(III) Complex

Inorganic Chemistry
Kaijie Ni, Christopher M Kozak

Abstract

A diamino-bis(phenolate) chromium(III) complex, CrCl(THF)[L], 1, where [L] = dimethylaminoethylamino- N, N-bis(2-methylene-4,6- tert-butylphenolate), has been synthesized in high yield and characterized by MALDI-TOF mass spectrometry, elemental analysis, UV-vis spectroscopy and single crystal X-ray diffraction. This complex combined with 4-dimethylaminopyridine (DMAP) or bis(triphenylphosphoranylidene)ammonium chloride or azide salts (PPNCl or PPNN3) shows improved activity over previously reported amine-bis(phenolate) chromium(III) complexes for copolymerization of cyclohexene oxide (CHO) and CO2to yield poly(cyclohexene) carbonate (PCHC). Kinetic studies of the complex/DMAP system showed the activation energy for polycarbonate formation to be 62 kJ/mol. End group analysis of resulting polycarbonates by MALDI-TOF MS reveals either the chloride of the Cr(III) complex or the external nucleophile initiates the copolymerization reaction.

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Citations

Apr 16, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Kenson AmbroseChristopher M Kozak
Nov 27, 2019·ChemSusChem·Jin HuangOlivier Coulembier

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