2018
DOI: 10.1021/acs.organomet.8b00554
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Manganese-Based Catalysts with Varying Ligand Substituents for the Electrochemical Reduction of CO2 to CO

Abstract: A series of manganese complexes were synthesized with a variety of ligands and ligand substituents. These complexes were then studied using ultraviolet–visible spectroscopy, cyclic voltammetry, density functional theory calculations, and bulk electrolysis. The UV–vis, cyclic voltammetry, and calculation data show that the bipyridine π* level is modulated by the incorporation of different substituents on the bipyridine and through this interaction moderates the observed catalytic activity of the complex toward … Show more

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Cited by 47 publications
(57 citation statements)
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“…Consistent with voltammetry and computational analysis presented below, the identical ν(CO) stretching modes illustrates the negligible electronic influence of the π-extended phen ligand in comparison to the bpy system. This observation is consistent with related reports of the analogous bromide complexes (Kurtz et al, 2015; Stanbury et al, 2017; Tignor et al, 2018). In contrast, the dmphen complex [3-CH 3 CN] + exhibits a descent in symmetry to pseudo-C s , evident in a breaking of degeneracy for its lower frequency asymmetric ν(CO) stretching modes, which occur at 1,959 and 1,944(sh) cm −1 .…”
Section: Resultssupporting
confidence: 93%
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“…Consistent with voltammetry and computational analysis presented below, the identical ν(CO) stretching modes illustrates the negligible electronic influence of the π-extended phen ligand in comparison to the bpy system. This observation is consistent with related reports of the analogous bromide complexes (Kurtz et al, 2015; Stanbury et al, 2017; Tignor et al, 2018). In contrast, the dmphen complex [3-CH 3 CN] + exhibits a descent in symmetry to pseudo-C s , evident in a breaking of degeneracy for its lower frequency asymmetric ν(CO) stretching modes, which occur at 1,959 and 1,944(sh) cm −1 .…”
Section: Resultssupporting
confidence: 93%
“…Three sequential one-electron cathodic peaks are observed at E pc = −1.48 V, −1.83 V and −2.94 V with only the third reduction exhibiting quasi-reversible behavior ( E 1/2 = −2.90 V, Δ E p = 81 mV at υ = 0.1 V s −1 ) vs. Fc +/0 . The phen complex, [2-CH 3 CN] + exhibits a first one-electron irreversible reduction at E pc = −1.48 V vs. Fc +/0 , identical to that observed for [1-CH 3 CN] + , further supporting the electronic similarity of bpy and phen at least in the [ fac- Mn(N ∧ N)(CO) 3 L] n class of complexes (Tignor et al, 2018). This first reduction has been previously established (Grills et al, 2018) as ligand-based according to an electrochemical-chemical ( EC ) reaction scheme whereby, upon one-electron reduction of the bpy π * orbital, rapid CH 3 CN dissociation occurs with a concurrent shift in radical character from the ligand to form the neutral five-coordinate 17-valence electron intermediate, [ fac- Mn 0 (bpy)(CO) 3 ] ( [1] 0 ).…”
Section: Resultssupporting
confidence: 60%
“…For example, we have recently used 4,4’-disubstituted-2,2’-bipyridyl ( R bpy) ligands to tune the photophysical properties and light-induced reactivity of Mn(CO) 3 X( R bpy) complexes [ 8 ] as well as to modulate the accessible pathways and efficiency of dihydrogen production by [Cp*Rh] complexes bearing R bpy ligands [ 9 ]. Such modifications have also been used to tune catalysis of carbon dioxide (CO 2 ) reduction to carbon monoxide (CO) by [Re(CO) 3 ] and [Mn(CO) 3 ] complexes [ 10 , 11 ]. With these observations and many others from the field, R bpy ligands have been found to be uniquely suited to systematic investigation of transition metal complexes.…”
Section: Introductionmentioning
confidence: 99%
“…[32] Hammett constants are trending in visualizing the effect of a range of ligands in a series of manganese based catalysts used for the electrochemical reduction of CO 2 . [33] The tunability of substituent control over the Co III/II redox potential is recognized by introducing Hammett constants for bis(dipyridylpyrrolide) cobalt complexes. [34] In a previous study by our group, it was recognized that the quantum mechanically derived MESP values can be served as an alternative for the experimental Hammett constants.…”
Section: Substituent Effectsmentioning
confidence: 99%