Mechanisms of Two-Electron versus Four-Electron Reduction of Dioxygen Catalyzed by Earth-Abundant Metal Complexes

ChemCatChem ◽  
2017 ◽  
Vol 10 (1) ◽  
pp. 9-28 ◽  
Author(s):  
Shunichi Fukuzumi ◽  
Yong-Min Lee ◽  
Wonwoo Nam
Keyword(s):  
Metal Complexes ◽  
Earth Abundant ◽  
Electron Reduction

Room Temperature Alkali Metal Reduction of Carbon Dioxide

2020 ◽  
Author(s):  
Lucas A. Freeman ◽  
Akachukwu D. Obi ◽  
Haleigh R. Machost ◽  
Andrew Molino ◽  
Asa W. Nichols ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Room Temperature ◽  
Chemical Reduction ◽  
Bond Cleavage ◽  
Open Shell ◽  
Metal Reduction ◽  
One Pot ◽  
Earth Abundant ◽  
Electron Reduction

The reduction of the relatively inert carbon–oxygen bonds of CO<sub>2</sub> to access useful CO<sub>2</sub>-derived organic products is one of the most important fundamental challenges in synthetic chemistry. Facilitating this bond-cleavage using earth-abundant, non-toxic main group elements (MGEs) is especially arduous because of the difficulty in achieving strong inner-sphere interactions between CO<sub>2</sub> and the MGE. Herein we report the first successful chemical reduction of CO<sub>2</sub> at room temperature by alkali metals, promoted by a cyclic(alkyl)(amino) carbene (CAAC). One-electron reduction of CAAC-CO<sub>2</sub> adduct (<b>1</b>) with lithium, sodium or potassium metal yields stable monoanionic radicals clusters [M(CAAC–CO<sub>2</sub>)]<sub>n</sub>(M = Li, Na, K, <b> 2</b>-<b>4</b>) and two-electron alkali metal reduction affords open-shell, dianionic clusters of the general formula [M<sub>2</sub>(CAAC–CO<sub>2</sub>)]<sub>n </sub>(<b>5</b>-<b>8</b>). It is notable that these crystalline clusters of reduced CO<sub>2</sub> may also be isolated via the “one-pot” reaction of free CO<sub>2</sub> with free CAAC followed by the addition of alkali metals – a reductive process which does not occur in the absence of carbene. Each of the products <b>2</b>-<b>8</b> were investigated using a combination of experimental and theoretical methods.<br>

scholarly journals Photoredox Catalysis with Metal Complexes Made from Earth-Abundant Elements

2017 ◽  
Vol 24 (9) ◽  
pp. 2039-2058 ◽  
Author(s):  
Christopher B. Larsen ◽  
Oliver S. Wenger
Keyword(s):  
Metal Complexes ◽  
Photoredox Catalysis ◽  
Earth Abundant

scholarly journals Mechanisms of catalytic reduction of CO2 with heme and nonheme metal complexes

2018 ◽  
Vol 9 (28) ◽  
pp. 6017-6034 ◽  
Author(s):  
Shunichi Fukuzumi ◽  
Yong-Min Lee ◽  
Hyun S. Ahn ◽  
Wonwoo Nam
Keyword(s):  
Metal Complex ◽  
Metal Complexes ◽  
Critical Review ◽  
Catalytic Reduction ◽  
Electron Reduction ◽  
Reduction Of Co2 ◽  
Metal Complex Catalysts

This critical review discusses the thermal and photocatalytic mechanisms of one-, two-, four-, six- and eight-electron reduction of CO2 with metal complex catalysts.

Earth-abundant metal complexes as catalysts for water oxidation; is it homogeneous or heterogeneous?

2015 ◽  
Vol 5 (11) ◽  
pp. 4901-4925 ◽  
Author(s):  
Md. Ali Asraf ◽  
Hussein A. Younus ◽  
Mekhman Yusubov ◽  
Francis Verpoort
Keyword(s):  
Metal Complexes ◽  
Water Oxidation ◽  
Earth Abundant

This minireview focuses on the aspects that determine whether particular catalysts for the oxidation of water are homogeneous or heterogeneous.

Transient FTIR spectroscopy after one- and two-colour excitation on a highly luminescent chromium(III) complex

2021 ◽  
Author(s):  
Pit Boden ◽  
Patrick Di Martino-Fumo ◽  
Gereon Niedner-Schatteburg ◽  
Wolfram Willy Seidel ◽  
Katja Heinze ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Ftir Spectroscopy ◽  
Transition Metal Complexes ◽  
Research Field ◽  
Earth Abundant ◽  
Photophysical Processes

The development of photoactive transition metal complexes with Earth-abundant metals is a rapidly growing research field, where a deeper understanding of the underlying photophysical processes is of great importance. A...

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