(Tetramethyltetraazaannulene)chromium Chloride:  A Highly Active Catalyst for the Alternating Copolymerization of Epoxides and Carbon Dioxide

A tetramethyltetraazaannulene complex incorporating a chromium(III) metal center has been shown to be highly active toward the copolymerization of cyclohexene oxide and carbon dioxide to afford poly(cyclohexene carbonate) in the presence of [PPN]N3 [PPN+ = bis(triphenylphosphoranylidene)ammonium] as...

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Bibliographic Details
Published in:Inorganic chemistry 2007-07, Vol.46 (14), p.5474-5476
Main Authors: Darensbourg, Donald J, Fitch, Shawn B
Format: Article
Language:English
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Summary:A tetramethyltetraazaannulene complex incorporating a chromium(III) metal center has been shown to be highly active toward the copolymerization of cyclohexene oxide and carbon dioxide to afford poly(cyclohexene carbonate) in the presence of [PPN]N3 [PPN+ = bis(triphenylphosphoranylidene)ammonium] as a cocatalyst. An asymptotical rate increase was observed, leveling at 2 equiv of cocatalyst with a maximum turnover frequency of 1300 h-1 at 80 °C. A benefit of this new catalyst system over that of the previously studied less-active (salen)CrX system is that the (tmtaa)CrCl catalyst has a much lower propensity toward the formation of a cyclic carbonate byproduct throughout the copolymerization reaction.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic7007842