Abstract
Single-component Cr(iii) catalysts for copolymerization of CO2 and cyclohexene oxide have been prepared. MALDI-TOF MS studies provide mechanistic information.
Highlights
The copolymerization of carbon dioxide (CO2) and epoxides has recently become a growing area of interest for several reasons
The reaction is an appealing alternative to the traditional method of polycarbonate synthesis, which involves the use of the endocrine disruptor Bisphenol-A and highly toxic phosgene.[1,2,3,4]
We previously reported the activity of amine-bis( phenolato) chromium(III) complexes for the copolymerization of epoxides and CO2 49–51 and the binding ability of DMAP to several derivatives of these ligands using matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry.[52]
Summary
The copolymerization of carbon dioxide (CO2) and epoxides has recently become a growing area of interest for several reasons. Initiation of epoxide ring opening by chloride nucleophiles is believed to dominate the reaction based on end-group analysis of the polymer by MALDI-TOF MS, where no DMAP-containing end-groups were observed.[49,52] Even for the faster second stage, the rate proved to be slower (robs = 0.75 × 10−2 min−1, Fig. S12†) than the rates with para-methoxy-containing 1·DMAP and 1·THF (3.5 × 10−2 min−1 and 1.2 × 10−2 min−1 respectively).
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