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Carbon Dioxide Fixation by Cycloaddition with Epoxides, Catalyzed by Biomimetic Metalloporphyrins
Author(s) -
Bai Dongsheng,
Duan Shuhui,
Hai Long,
Jing Huanwang
Publication year - 2012
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201200204
Subject(s) - chemistry , cycloaddition , catalysis , propylene oxide , propylene carbonate , selectivity , medicinal chemistry , carbon fixation , tribromide , epoxide , porphyrin , cyclohexene oxide , polymer chemistry , inorganic chemistry , organic chemistry , carbon dioxide , copolymer , polymer , ethylene oxide , electrode , electrochemistry
Several biomimetic metalloporphyrin complexes (M(TPP)XY; in which TPP= meso ‐porphyrin; M=Mg II , Al III , Sn II , or Sn IV ; X=OAc, F, Cl, Br, I, OTf, or none; and Y=Cl, Br, I, OTf, or none) were prepared, characterized, and used effectively in the “green” synthesis of cyclic carbonates from epoxides and CO 2 . The catalytic systems of Mg(TPP)/tetrabutylammonium iodide and Al(TPP)Cl/phenyltrimethyl ammonium tribromide can initiate the cycloaddition of epoxides and CO 2 at room temperature to generating cyclic carbonates in excellent yield. Chlorophyll A is shown to induce enantioselectivity of racemic propylene oxide. All reactions displayed excellent selectivity to cyclic carbonate without polycarbonate and other by‐products. Chloropropylene carbonate is shown to be obtained under CO 2 bubbling conditions catalyzed by Al(TPP)Cl/phenyltrimethylammonium tribromide. The catalytic order of activity for biomimetic metalloporphyrins is Al III >Mg II >Sn IV >Sn II . These phenomena are explained with respect to the Lewis acidity of metal center in metalloporphyrins.