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Dinitrosyl Iron Complex [K‐18‐crown‐6‐ether][(NO) 2 Fe( Me PyrCO 2 )]: Intermediate for Capture and Reduction of Carbon Dioxide
Author(s) -
Tseng YuTing,
Ching WeiMin,
Liaw WenFeng,
Lu TsaiTe
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202002977
Subject(s) - chemistry , reactivity (psychology) , oxalate , nucleophile , catalysis , lewis acids and bases , redox , medicinal chemistry , carboxylate , selective reduction , inorganic chemistry , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
Abstract Continued efforts are made for the utilization of CO 2 as a C 1 feedstock for regeneration of valuable chemicals and fuels. Mechanistic study of molecular (electro‐/photo‐)catalysts disclosed that initial step for CO 2 activation involves either nucleophilic insertion or direct reduction of CO 2 . In this study, nucleophilic activation of CO 2 by complex [(NO) 2 Fe(μ‐ Me Pyr) 2 Fe(NO) 2 ] 2− ( 2 , Me Pyr=3‐methylpyrazolate) results in the formation of CO 2 ‐captured complex [(NO) 2 Fe( Me PyrCO 2 )] − ( 2‐CO 2 , Me PyrCO 2 =3‐methyl‐pyrazole‐1‐carboxylate). Single‐crystal structure, spectroscopic, reactivity, and computational study unravels 2‐CO 2 as a unique intermediate for reductive transformation of CO 2 promoted by Ca 2+ . Moreover, sequential reaction of 2 with CO 2 , Ca(OTf) 2 , and KC 8 established a synthetic cycle, 2 → 2‐CO 2 → [(NO) 2 Fe(μ‐ Me Pyr) 2 Fe(NO) 2 ] ( 1 ) → 2 , for selective conversion of CO 2 into oxalate. Presumably, characterization of the unprecedented intermediate 2‐CO 2 may open an avenue for systematic evaluation of the effects of alternative Lewis acids on reduction of CO 2 .