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Preparation of 6-aminocyclohepta-2,4-dien-1-one Derivatives via Tricarbonyltroponeiron
Published on: August 12, 2019
Dinitrosyl Iron Complex [K-18-crown-6-ether][(NO)2 Fe(Me PyrCO2 )]: Intermediate for Capture and Reduction of Carbon
Yu-Ting Tseng1,2, Wei-Min Ching3, Wen-Feng Liaw2
1Department of Chemistry, Chung Yuan Christian University, Taoyuan, 32023, Taiwan.
Abstract:
Continued efforts are made for the utilization of CO2 as a C1 feedstock for regeneration of valuable chemicals and fuels. Mechanistic study of molecular (electro-/photo-)catalysts disclosed that initial step for CO2 activation involves either nucleophilic insertion or direct reduction of CO2 . In this study, nucleophilic activation of CO2 by complex [(NO)2 Fe(μ-Me Pyr)2 Fe(NO)2 ]2- (2, Me Pyr=3-methylpyrazolate) results in the formation of CO2 -captured complex [(NO)2 Fe(Me PyrCO2 )]- (2-CO2 , Me PyrCO2 =3-methyl-pyrazole-1-carboxylate). Single-crystal structure, spectroscopic, reactivity, and computational study unravels 2-CO2 as a unique intermediate for reductive transformation of CO2 promoted by Ca2+ . Moreover, sequential reaction of 2 with CO2 , Ca(OTf)2 , and KC8 established a synthetic cycle, 2 → 2-CO2 → [(NO)2 Fe(μ-Me Pyr)2 Fe(NO)2 ] (1) → 2, for selective conversion of CO2 into oxalate. Presumably, characterization of the unprecedented intermediate 2-CO2 may open an avenue for systematic evaluation of the effects of alternative Lewis acids on reduction of CO2 .
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