Effect of Transition Metal Variability in NNN-Pincer Complexes on Catalytic CO2 Reduction to Methanol.

IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Saurabh Vinod Parmar, Vidya Avasare
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引用次数: 0

Abstract

The catalytic efficiency of M-H2tpda pincer complexes (M=Mn(I), Fe(II), Co(III)) in CO2 hydrogenation, emphasizing the role of transition metal variability have been discussed. The DFT analysis demonstrates that complexes with low αR values form weaker M-H bonds, enhancing catalyst reactivity with the elongation of M-H bond. The analysis further displays excellent catalytic performance for Mn-H2tpda (ΔE=20.3 kcal/mol), Fe-H2tpda (ΔE=21.0 kcal/mol) and Co-H2tpda (ΔE=23.6 kcal/mol) for CO2 to formic acid formation. The Co-H2tpda (ΔE=16.7 kcal/mol) is comparatively better than Mn-H2tpda (ΔE=20.7 kcal/mol) and Fe-H2tpda (ΔE=19.6 kcal/mol) in formaldehyde formation. All three catalysts exhibit excellent catalytic performance in the conversion of formaldehyde to methanol. The condensed Fukui function calculations of these catalyst complexes establish direct relationship between the ΔE for the rate limiting catalytic cycle and the electrophilicity of the metal centers. The TOF calculations further helped to understand the catalytic performance of the catalysts at various temperatures.

nnn -钳形配合物中过渡金属变异性对CO2催化还原甲醇的影响。
讨论了M- h2tpda钳形配合物(M = Mn(I), Fe(II), Co(III))在CO2加氢中的催化效率,强调了过渡金属中心变异性的作用。DFT分析表明,αR值较低的配合物形成较弱的M-H键,随着M-H键的延长,催化剂的反应活性增强。进一步分析表明,Mn-H2tpda (ΔE = 20.3 kcal/mol)、Fe-H2tpda (ΔE = 21.0 kcal/mol)和Co-H2tpda (ΔE = 23.6 kcal/mol)对CO2生成甲酸具有优异的催化性能。Co-H2tpda (ΔE = 16.7 kcal/mol)在甲醛生成方面优于Mn-H2tpda (ΔE = 20.7 kcal/mol)和Fe-H2tpda (ΔE = 19.6 kcal/mol)。这三种催化剂在甲醛转化为甲醇的过程中均表现出优异的催化性能。这些催化剂配合物的浓缩福井函数计算建立了极限催化循环的ΔE与金属中心的亲电性之间的直接关系。TOF计算有助于进一步了解催化剂在不同温度下的催化性能。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemistry - An Asian Journal
Chemistry - An Asian Journal 化学-化学综合
CiteScore
7.00
自引率
2.40%
发文量
535
审稿时长
1.3 months
期刊介绍: Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).
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