Dinitrosyl Iron Complex [K-18-crown-6-ether][(NO) 2 Fe( Me PyrCO 2 )]: Intermediate for Capture and Reduction of Carbon Dioxide.

Autor: Tseng YT; Department of Chemistry, Chung Yuan Christian University, Taoyuan, 32023, Taiwan.; Department of Chemistry, National Tsing Hua University, Hsinchu, 30013, Taiwan., Ching WM; Institute of Chemistry, Academia Sinica, Taipei, 10529, Taiwan., Liaw WF; Department of Chemistry, National Tsing Hua University, Hsinchu, 30013, Taiwan., Lu TT; Department of Chemistry, Chung Yuan Christian University, Taoyuan, 32023, Taiwan.; Institute of Biomedical Engineering, National Tsing Hua University, Hsinchu, 30013, Taiwan.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2020 Jul 13; Vol. 59 (29), pp. 11819-11823. Date of Electronic Publication: 2020 May 18.
DOI: 10.1002/anie.202002977
Abstrakt: 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 .
(© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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