Electrochemical behaviors of a pincer-type NNN-Fe complex and catalytic H₂ evolution activity

Abstract

We describe electrochemical reactivity of a pincer-type [NNN-Fe(tBuNC)3](ClO4)2 complex. Upon electron-reduction, the Fe(I) species experienced disproportionation to Fe(0) and Fe(II). The electron-reduced Fe center dissociated a tBuNC ligand to make...

Two-Electron-Induced Reorganization of Cobalt Coordination and Metal–Ligand Cooperative Redox Shifting Co(I) Reactivity toward CO2 Reduction

“…Previous NNN-pincer type complexes exhibited HER activity, 39,40 S1). The Co−NCCH 3 bonds in [2- 3) (all potentials reported here are vs Fc 0/+ ) and peak to peak separation values (ΔE p ) between 80 and 90 mV at 100 mV/s (Table S2).…”

“…Previous NNN-pincer type complexes exhibited HER activity, , for example, [NNN NCH 3 –Co­(CH 3 CN) 3 ]­(PF 6 ) 2 ([ 1-(CH 3 CN) 3 ]­(PF 6 ) 2 ) showed the turnover frequency (TOF) of ∼10 2 for reduction of acetic acid. However, the enclosure of the Co center with 1,10-phenanthroline (phen) ligand as [NNN NCH 3 –Co­(phen) (CH 3 CN)]­(PF 6 ) 2 ([ 2-CH 3 CN ]­(PF 6 ) 2 ) severely decreased the TOF H2 value of HER to 6 s –1 (Figure S1).…”

Metal complexes containing silicon‐based pincer ligands: Reactivity and application in small molecule activation

“…6 Moreover, there has been a series of reports on pincer complexes mimicking the local geometry and reactivity of enzymes. [7][8][9][10][11][12][13] A pincer ligand generally consists of a central monoanionic (or neutral) anchoring donor atom and flanking donor atoms connected through an organic backbone. 14 After the first report of a [PCP]-type pincer ligand by Moulton and Shaw, 15 a number of pincer ligands were synthesized by substituting the donor atoms with N, O, P, S, and so on.…”

“…Metal complexes supported by pincer ligands have already been utilized in various catalytic chemical conversions 6 . Moreover, there has been a series of reports on pincer complexes mimicking the local geometry and reactivity of enzymes 7–13 …”

Electrocatalytic Hydrogen Evolution by Water‐Soluble Cobalt (II), Copper (II) and Iron (III)meso‐Tetrakis(carboxyl)porphyrin

“…In the past few decades, the most effective catalysts are still based on precious metals, such as Pt, [6] Ru, Re [7] and Ir, which are not a sustainable resource. [8] Recently, a majority of first-row transition metal complexes have been studied either as photocatalysts or electrocatalysts for hydrogen production, such as Fe, [9,10] Cu [11][12][13] and Co [14][15][16] complexes.Currently, most of these complexes use organic acids as a proton source to drive hydrogen evolution. Clearly, those catalysts which can directly drive water splitting to produce hydrogen are more attractive in terms of renewable energy sources and environmental friendly.…”