Kim, HS Kim, JJ Lee, SD Lah, MS Moon, D Jang, HG 2024-01-21T09:14:25Z 2024-01-21T09:14:25Z 2021-09-03 2003-02-03 0947-6539 https://pubs.kist.re.kr/handle/201004/138825 Coupling reactions Of CO2 and epoxide to produce cyclic carbonates were performed in the presence of a catalyst [L2ZnX2] (L = pyridine or substituted pyridine; X Cl, Br, 1), and the effects of pyridine and halide ligands on the catalytic activity were investigated. The catalysts with electron-donating substituents on pyridine ligands exhibit higher activity than those with unsubstituted pyridine ligands. On the other hand, the catalysts with electron-withdrawing substituents at the 2-position of the pyridine ligands show no activity; this demonstrates the importance of the basicity of the pyridine ligands. The catalytic activity of [L2ZnX2] was found to decrease with increasing electronegativity of the halide ligands. A series of highly active zinc complexes bridged by pyridinium alkoxy ions of the general formula [{(mu-OCHRCH2L)ZnBr2}(n)] (n=2 for R=CH3; n=3 for R=H; L=pyridine or substituted pyridine) were synthesized and characterized by X-ray crystallography. The dinuclear zinc complexes obtained from propylene oxide adopt a square-planar geometry for the Zn2O2 core with two bridging pyridinium propoxy ion ligands. Trinuclear zinc complexes prepared from ethylene oxide adopt a boat geometry for the Zn3O3 core, in which three zinc and three oxygen atoms are arranged in an alternate fashion. These zinc complexes bridged by pyridinium alkoxy ions were also isolated from the coupling reactions Of CO2 and epoxides performed in the presence of [L2ZnBr2]. Rapid CO2 insertion into the zinc-oxygen bond of the zinc complexes bridged by pyridinium alkoxy ions leads to the formation of zinc carbonate species; these which yield cyclic carbonates and zinc complexes bridged by pyridinium alkoxy ions upon interaction with epoxides. The mechanistic pathways for the formation of active species and cyclic carbonates are discussed on the basis of results from structural and spectroscopic analyses. English WILEY-V C H VERLAG GMBH CARBON-DIOXIDE ALTERNATING COPOLYMERIZATION CYCLIC CARBONATES TETRAAZACYCLOALKANE COMPLEXES KINETIC RESOLUTION CATALYTIC-ACTIVITY TERPOLYMERIZATION PHENOXIDES FIXATION CADMIUM New mechanistic insight into the coupling reactions CO2 and epoxides in the presence of zinc complexes Article 10.1002/chem.200390076 1 CHEMISTRY-A EUROPEAN JOURNAL, v.9, no.3, pp.678 - 686 CHEMISTRY-A EUROPEAN JOURNAL 9 3 678 686 scie scopus 000180868800011 2-s2.0-0037415846 Chemistry, Multidisciplinary Chemistry Article CARBON-DIOXIDE ALTERNATING COPOLYMERIZATION CYCLIC CARBONATES TETRAAZACYCLOALKANE COMPLEXES KINETIC RESOLUTION CATALYTIC-ACTIVITY TERPOLYMERIZATION PHENOXIDES FIXATION CADMIUM alkylene carbonate carbon dioxide fixation epoxides green chemistry homogenous catalysis