Syntheses of bis(organomercury)1,3-dithiole-2-thione-4,5-dithiolates and related compounds: Crystal structure of bis(phenylmercury)1,3-dithiole-2-one-4,5-dithiolate

Martins, Carolina X.; Ferreira, Gláucio B.; Howie, R. Α.; Bordinhão, Jairo; Comerlato, Nadia M.; Wardell, Jámes L.; Wardell, Solange M. S. V.

doi:10.1016/j.ica.2014.12.037

Cited by 6 publications

(1 citation statement)

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“…This sulfurrich heterocyclic ligand has strong affinities binding to metal ions and demonstrates reversible redox properties. [41] In recent years, a considerable amount of interest has been placed on this dmit complexes [41][42][43][44][45][46] and their applications in organic conductors, [41,47,48] chemical sensors, [49,50] magnetic materials, [42,43] and nonlinear optical materials. [44,49,[51][52][53] As an analogous to dmit, the maleonitriledithiolate (mnt 2− ) complexes also attracted some attentions for the prominent biomimetic and redox properties.…”

Section: Introductionmentioning

confidence: 99%

Heteroleptic dmit nickel complexes with bis(diphenylphosphanyl)amine ligands as robust molecular electrocatalysts for hydrogen evolution

Xie

Cao

et al. 2020

Applied Organom Chemis

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Four new neutral heteroleptic dmit nickel complexes bearing bis(diphenylphosphanyl)amine ligands, [RN (PPh 2) 2 Ni(dmit)] (where dmit 2− = 1,-3-dithiole-2-thione-4,5-dithiolate; R = (CH 2) 4 CH 3 [1], (CH 2) 3 OCH 3 [2], (CH 2) 2 CH (CH 3) 2 [3], and CHPhCH 3 [4]), have been synthesized in moderated yields by the reactions between (n-Bu) 2 Sn(dmit) and RN (PPh 2) 2 NiCl 2 at room temperature. The complexes were fully characterized by elemental analysis, spectroscopy (Fourier transform infrared [FTIR], ultraviolet-visible [UV-vis], 1 H, 13 C{ 1 H}, and 31 P{ 1 H} nuclear magnetic resonance [NMR]), thermogravimetric analysis, and single crystal X-ray diffraction. In the crystal structures of 1-3 and 4Á2CH 2 Cl 2 , every nickel atom adopts a slightly distorted square-planar coordination by two phosphorus atoms of the RN (PPh 2) 2 ligand and two sulfur atoms of the dmit ligand. Furthermore, the electrochemical behaviors and electrocatalytic activities of 1-4 for hydrogen evolution have also been investigated by the cyclic voltammetry using trifluoroacetic acid (TFA) as the proton source. With the addition of 120-mM trifluoroacetic acid to 0.5-mM 1-4 in MeCN, the turnover frequency values of these catalysts were estimated to be 2827-5149 s −1 , and the relevant overpotentials were 0.72-0.79 V. Density functional theory (DFT) calculations and electrochemical investigations suggest that H 2 production proceeds via a key hydride intermediate [NiH (SH)] with an adjacent protonated sulfur atom of the dmit ligand in which the chelating sulfur atoms serve as proton relays. These findings demonstrate that these heteroleptic dmit nickel complexes could serve as robust and effective molecular electrocatalysts for hydrogen evolution.

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