Cobaltoporphyrin-Catalyzed CO 2 /Epoxide Copolymerization: Selectivity Control by Molecular Design

Carly E. Anderson, Sergei I. Vagin, Wei Xia, Hanpeng Jin, Bernhard Rieger

Research output: Contribution to journalArticlepeer-review

102 Scopus citations


A series of cobalt(III) chloride porphyrin complexes of the general formula 5,10,15,20-tetra(p-alkoxy)phenylporphyrin cobalt chloride (4b-e) and the related 5,10,15,20-tetra(p-nitro)phenylporphyrin cobalt chloride (4f) are presented and their reactivity toward propylene oxide (PO)/CO 2 coupling/copolymerization is explored. While the nitro-substituted complex (4f), in conjunction with an onium salt, shows moderate activity toward cyclization, the 4b-e/onium systems show superior copolymerization activity in comparison to tetraphenylporphyrin Co(III) chloride (4a) with high selectivity and conversion to poly(propylene carbonate) (PPC). A comprehensive copolymerization behavior study of the alkoxy-substituted porphyrin complexes 4b-e in terms of reaction temperature and CO 2 pressure is presented. Complexes bearing longer alkoxy-substituents demonstrate the highest polymerization activity and molecular weights, however all substituted catalyst systems display a reduced tolerance to increased temperature with respect to PPC formation. Studies of the resulting polymer microstructures show excellent head-to-tail epoxide incorporation and near perfectly alternating poly(carbonate) character at lower polymerization temperatures. © 2012 American Chemical Society.
Original languageEnglish (US)
Pages (from-to)6840-6849
Number of pages10
Issue number17
StatePublished - Aug 21 2012
Externally publishedYes


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