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Updated: Jul 7, 2026

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Carbonylative polymerization of oxetanes initiated by acetyl cobalt complexes
Yessi Permana1, Koji Nakano, Makoto Yamashita
1Department of Chemistry and Biotechnology, Graduate School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan.
Abstract:
Four acetyl cobalt complexes, [AcCo(CO)(3)P(p-tolyl)(3)] (1; p-tolyl=4-Me-C(6)H(4)), [AcCo(CO)(3)P(OPh)(3)] (2), [AcCo(CO)(3)P(NMe(2))(3)] (3), and [AcCo(CO)(2)(dppp)] (4; dppp=1,3-bis(diphenylphosphanyl)propane), were synthesized, characterized, and examined as catalysts for the unprecedented carbonylative polymerization of oxetanes. Copolymers containing ester (4-hydroxyalkanoate) and/or ether units were obtained with complexes 1 and 2, but not with complexes 3 and 4 either in the presence or absence of additional phosphorus ligands. The ester unit/ether unit ratio varied in the range 21:79-63:37, and the highest ester/ether ratio of 63:37 was achieved by using complex 1 in the presence of a further 5 equivalents of P(OPh)(3). Although direct carbonylative polymerization is possible, preformation and ring opening of the gamma-lactone is also suggested as an alternative pathway.
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