{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T11:11:31Z","timestamp":1760267491964,"version":"build-2065373602"},"reference-count":54,"publisher":"MDPI AG","issue":"7","license":[{"start":{"date-parts":[[2017,7,14]],"date-time":"2017-07-14T00:00:00Z","timestamp":1499990400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Catalysts"],"abstract":"<jats:p>Metal complexes of meso-arylporphyrins (Cr(III), Fe(III), and Zn(II)) were evaluated in the coupling reaction of cyclohexene oxide (CHO) with CO2 in compressed medium, where the Cr complexes were demonstrated to be the most active systems, leading predominantly to copolymerisation products. It is noteworthy that no addition of solvent was required. To improve the catalytic activity, and to simultaneously increase the solubility in compressed CO2, a new fluorinated catalyst, tetrakis(4-trifluoromethylphenyl)porphyrinatochromium(III) chloride (CrCl-pCF3TPP), was applied to this reaction. The alternating copolymerisation of CHO with CO2, using the Cr(III) fluorinated porphyrin catalyst, required the use of a co-catalyst, bis(triphenylphosphine)iminium chloride (PPNCl), with the best yields of copolymers being obtained at 80 \u00b0C, and CO2 pressures in the range of 50\u2013110 bar, over a period of 24 h, with a low catalyst\/substrate molar ratio (0.07%). The polycarbonate\u2019s structure was analysed by 1H NMR, 13C NMR, and MALDI-TOF spectroscopy, which demonstrated high carbonate incorporations (98\u201399%). Gel permeation chromatography revealed number-average molecular weights (Mn) in the range of 4800\u201312,800 and narrow molecular weight distributions (Mw\/Mn \u2264 1.63).<\/jats:p>","DOI":"10.3390\/catal7070210","type":"journal-article","created":{"date-parts":[[2017,7,14]],"date-time":"2017-07-14T10:45:02Z","timestamp":1500029102000},"page":"210","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":19,"title":["Solventless Coupling of Epoxides and CO2 in Compressed Medium Catalysed by Fluorinated Metalloporphyrins"],"prefix":"10.3390","volume":"7","author":[{"given":"Rui","family":"Carrilho","sequence":"first","affiliation":[{"name":"CQC, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal"},{"name":"Department of Physical and Inorganic Chemistry, University Rovira i Virgili, Marcel\u00b7l\u00ed Domingo, Tarragona 43007, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2858-7539","authenticated-orcid":false,"given":"Lucas","family":"Dias","sequence":"additional","affiliation":[{"name":"CQC, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal"}]},{"given":"Raquel","family":"Rivas","sequence":"additional","affiliation":[{"name":"Department of Physical and Inorganic Chemistry, University Rovira i Virgili, Marcel\u00b7l\u00ed Domingo, Tarragona 43007, Spain"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4958-7677","authenticated-orcid":false,"given":"Mariette","family":"Pereira","sequence":"additional","affiliation":[{"name":"CQC, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal"}]},{"given":"Carmen","family":"Claver","sequence":"additional","affiliation":[{"name":"Department of Physical and Inorganic Chemistry, University Rovira i Virgili, Marcel\u00b7l\u00ed Domingo, Tarragona 43007, Spain"},{"name":"Centre Tecnol\u00f2gic de la Qu\u00edmica, Marcel\u00b7l\u00ed Domingo s\/n, Campus Sescelades, Tarragona 43007, Spain"}]},{"given":"Anna","family":"Masdeu-Bult\u00f3","sequence":"additional","affiliation":[{"name":"Department of Physical and Inorganic Chemistry, University Rovira i Virgili, Marcel\u00b7l\u00ed Domingo, Tarragona 43007, Spain"}]}],"member":"1968","published-online":{"date-parts":[[2017,7,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"1748","DOI":"10.1055\/s-0033-1339483","article-title":"Catalyst development in the context of ring expansion-addition of carbon dioxide to epoxides to give organic carbonates","volume":"24","author":"Whiteoak","year":"2013","journal-title":"Synlett"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1312","DOI":"10.1039\/b819997c","article-title":"The synthesis of organic carbonates from carbon dioxide","volume":"21","author":"Sakakura","year":"2009","journal-title":"Chem. 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