Homoleptic Ni(ii) dithiocarbamate complexes as pre-catalysts for the electrocatalytic oxygen evolution reaction

Abstract

Four new functionalized Ni(II) dithiocarbamate complexes of the formula [Ni(Lx)2] (1-4) (L1 = N-methylthiophene-N-3-pyridylmethyl dithiocarbamate, L2 = N-methylthiophene-N-4-pyridylmethyl, L3 = N-benzyl-N-3-pyridylmethyl dithiocarbamate, and L4 = N-benzyl-N-4-pyridylmethyl dithiocarbamate) have been synthesized...

Antiproliferative activity of Fe(ii), Co(ii), Ni(ii), Cu(ii), and Zn(ii) complexes of dithiocarbamate: synthesis, structural characterization, and thermal studies

“…After complexation, these frequencies are observed at higher wavenumbers, which may be attributed to the π delocalization of the lone pair electrons of nitrogen over the -NCS 2 backbone. 35 The IR spectra of the ligand and its complexes 1-5 are provided in the ESI (Fig. S1 †).…”

Insights into the supramolecular and molecular electrocatalytic properties of 1,2-bis(diphenylphosphine)ethane appended nickel(ii) 1,2-dithiosquarate for oxygen and hydrogen evolution reactions

“…9 and Table 5). 17,18 H 3 O + + e − + M → M–H ads + H 2 O (step 1)M–H ads + M–H ads → H 2 (Step 2: Tafel step)M–H ads + H + e − → H 2 (step 3: Volmer–Heyrovsky step)…”

“…14 The unusual redox properties in this class of compounds are due to the non-innocent character originating from their quasi-aromaticity and strong π-electron donor ability due to the involvement of sulfur atoms. 14–18 The avid interest in such molecule based metal complexes stems from the following reasons: (a) they have tuneable steric and electronic structures, (b) adaptable intrinsic activity, (c) clearly defined catalytic mechanisms, (d) high product selectivity and (e) excellent atomic economy. 15 Inspired by these aspects associated with metal dithiolenes/dithiolates, we recently have explored their utility as molecular electrocatalysts for the oxygen evolution reaction (OER).…”

The rigidity and chelation effect of ligands on the hydrogen evolution reaction catalyzed by Ni(ii) complexes

“…The bidentate 1,1-dithiolate complexes with various metal ions, exhibiting square planar geometry, have been reported and extensively studied for structural variation, bonding ability, and redox chemistry with their application as photocatalysts and electrocatalysts for energy generation processes. 24 Ni-based dithiolate complexes exhibit promising H 2 production ability and act as molecular catalysts offering significant advantages in terms of ease of structural modifications to tune the stability, redox properties, and electrocatalytic activity. 25,26 DuBois and co-workers have employed internal proton relays in the second coordination sphere of Ni phosphine-based complexes to design extremely fast catalysts and demonstrated a Ni(N 2 P 2 ) electrocatalyst with a turnover frequency (TOF) above 10 5 s −1 for H 2 production.…”