Electrocatalytic CO<sub>2</sub> Reduction to Formate with Molecular Fe(III) Complexes Containing Pendent Proton Relays
作者:Asa W. Nichols、Shelby L. Hooe、Joseph S. Kuehner、Diane A. Dickie、Charles W. Machan
DOI:10.1021/acs.inorgchem.9b03341
日期:2020.5.4
Fe-bound O atoms upon reduction of the Fe center. Here, we report the synthesis, structural characterization, and reactivity of two iron(III) compounds with 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(2-methoxy-4-methylphenol) (mecrebpy[H]2, Fe(mecrebpy)Cl, 2) and 6,6'-([2,2'-bipyridine]-6,6'-diyl)bis(4-(tert-butyl)benzene-1,2-diol) (tbucatbpy[H]4, Fe(tbucatbpy), 3) as ligands, where pendent -OMe and -OH groups
以前,我们报道了以6,6'-([[2,2'-联吡啶] -6,6'-二基)双(2,4-二叔丁基苯酚)作为配体的铁(III)配合物(Fe(tbudhbpy )Cl,1)具有催化作用,可将CO2电化学还原成甲酸酯(法拉第效率FEHCO2- = 68±4%)。在机械实验中,发现基本成分是预平衡反应,涉及质子供体与催化剂的缔合,该反应在质子中心还原后将质子转移到与铁结合的O原子上。在这里,我们报告了两种铁(III)化合物与6,6'-([[2,2'-联吡啶] -6,6'-二基)双(2-甲氧基-4-)的合成,结构表征和反应性甲基苯酚)(Mecrebpy [H] 2,Fe(Mecrebpy)Cl,2)和6,6'-([2,2'-联吡啶] -6,6'-二基)双(4-(叔丁基)苯-1,2-二醇)(tbucatbpy [H] 4,Fe(tbucatbpy),3)作为配体,其中侧的-OMe和-OH基团准备改变涉及F