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Carbonylative Polymerization of Oxetanes Initiated by Acetyl Cobalt Complexes
Author(s) -
Permana Yessi,
Nakano Koji,
Yamashita Makoto,
Watanabe Daisuke,
Nozaki Kyoko
Publication year - 2008
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200700339
Subject(s) - cobalt , ether , chemistry , polymerization , polymer chemistry , propane , catalysis , copolymer , medicinal chemistry , organic chemistry , polymer
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 γ‐lactone is also suggested as an alternative pathway.