Nickel Complexes Based on Thiophosphorylated Calix[4]Resorcinols as Effective Catalysts for Hydrogen Evolution

Khrizanforova, Vera V.; Knyazeva, Irina R.; Sokolova, V. I.; Nizameev, Irek R.; Gryaznova, T. V.; Kadirov, Marsil K.; Бурилов, А. Р.; Sinyashin, Оleg G.; Budnikova, Yulia H.

doi:10.1007/s12678-015-0251-4

Cited by 19 publications

(6 citation statements)

References 57 publications

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“…At present, the primary challenge to widespread applications of hydrogen energy is to develop efficient catalysts for proton reduction using abundant metals instead of expensive noble metal, such as platinum. On this demand, a large number of transition mental complexes, such as nickel [4–6] and cobalt, [7–9] demonstrated excellent catalytic activity for hydrogen evolution and received much more attentions. Furthermore, in these reported homogeneous hydrogen‐evolving catalysts, most complex catalysts usually operate in organic solvents or the mixtures of organic solvent and water because of their poor solubility and aqueous activity [10–14] …”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Hydrogen Evolution Catalyzed by 3,4‐Toluenedithiolate Nickel Complexes of Bis(diphenylphosphine)amine Ligand Containing An Azahydrophilic Group

Xie

Zhang

et al. 2021

ChemCatChem

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Two 3,4‐toluenedithiolate nickel complexes of bis(diphenylphosphine)amine ligand containing an azahydrophilic group, [(CH3)2N(CH2)2N(PPh2)2Ni(tdt)] (1) and [(CH3)2N+Bz(CH2)2N(PPh2)2Ni(tdt)] Br− (2) (tdt=3,4‐toluenedithiolate, Bz=PhCH2), have been synthesized and characterized by elemental analysis and spectroscopy (FTIR, UV‐vis, 1H, and 31P{1H} NMR). The electrochemical property of 1 and 2 was investigated in MeCN and MeCN/H2O, respectively. The redox potentials of 1 and 2 are shifted to less‐negative potentials as the water contents increase in MeCN/H2O, in which the first reduction potentials for 1 and 2 are shifted positively by 160 and 140 mV in 7 : 3 MeCN/H2O in compassion to neat MeCN. 1 and 2 exhibit the electrocatalysis for hydrogen (H2) evolution using trifluoroacetic acid (TFA) as the proton source both in MeCN and in MeCN/H2O. Remarkably, 1 and 2 display favorable energetics towards electrocatalytic proton reduction in the presence of water, and the more hydrophilic quaternary ammonium group is beneficial to enhance the catalytic activity for 2. A CEEC (C is a chemical step protonation and E is the electrochemical step reduction) electrocatalytic mechanism for hydrogen production by 1 was proposed in MeCN, where the catalyst 1 firstly undergo rapidly protonation at the coordinating S1 atom in the tdt ligand to generate intermediate [NiIIS1‐H]+ before undergoing reduction, and the reduction of [NiIIS1‐H]+ yields a key metal hydride species, [NiIII‐H]. Theoretical calculations carried out using density functional theory (DFT) which is consistent with the proposed catalytic reaction mechanism for 1.

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Section: Introductionmentioning

confidence: 99%

Electrocatalytic Hydrogen Evolution Catalyzed by 3,4‐Toluenedithiolate Nickel Complexes of Bis(diphenylphosphine)amine Ligand Containing An Azahydrophilic Group

Xie

Zhang

et al. 2021

ChemCatChem

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“…Dihydrogen is an environmentally friendly energy carrier as upon combustion it only produces H 2 O, In order to enable the establishment of a society based on dihydogen as an energy source, for many years researchers have focused on the search for efficient proton‐reduction catalysts, notably for catalysts that are not based on noble metals . In the field of bioinorganic chemistry the synthesis of structural models of hydrogenases is a common strategy to devise molecular catalysts for proton reduction , .…”

Section: Introductionmentioning

confidence: 99%

Nickel Complexes of Pyridine‐Functionalized N‐Heterocyclic Carbenes: Syntheses, Structures, and Activity in Electrocatalytic Hydrogen Production

2016

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“…It is therefore essential to develop efficient and more stable catalysts for hydrogen production that contain earth-abundant and cheap metals that are easy to synthesize with inexpensive components. [12][13][14] With this in mind, a great number earth-abundant transition metal complexes, such as nickel, [14][15][16][17][18][19][20] cobalt, [21][22][23][24] copper, [21,25,26] and zinc, [21] have been developed recently as molecular electrocatalysts for hydrogen evolution.…”

Section: Introductionmentioning

confidence: 99%

“…[43,44] Khrizanforova et al have described that the nickel complexes of the thiophosphorylated calix [4]resorcinol demonstrate high catalytic activity for hydrogen evolution in the presence of TFA and stability in the electrocatalysis at both glassy carbon (GC) and Hg pool electrodes. [18] Because of the P S fragment in the thiophosphorylated calix [4]resorcinol ligand, the nickel atom is in a S 4 coordination sphere, leading to the nickel complexes can mimic the active sites of [NiFe]-hydrogenases, in which the nickel atom is also coordinated to four sulfur atoms. [7] The aminodiphosphine monosulfide as a hemilabile ligand continues to attract much attentions owing to the diversity in the coordination modes (mainly incorporate the P-monodentate and the hybrid P,S-chelate ligands).…”

Section: Introductionmentioning

confidence: 99%

Heteroleptic nickel complexes bearing O‐methyldithiophosphate and aminodiphosphine monosulfide ligands as robust molecular electrocatalysts for hydrogen evolution

Chen

Xie

et al. 2022

Applied Organom Chemis

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Five new heteroleptic nickel complexes containing O‐methyldithiophosphate and aminodiphosphine monosulfide ligands, [Ni((PPh2)({S}PPh2)NR)(S2P{O}OCH3)] (R = (CH2)4CH3 (1), (CH2)3OCH3 (2), (CH2)3SCH3 (3), (CH2)2CH(CH3)2 (4), and C6H4CH3–4 (5)), were synthesized by two different methods at room temperature. All complexes were characterized by elemental analysis, spectroscopy (1H, 13C, 31P nuclear magnetic resonance [NMR], and ultraviolet–visible [UV–vis]), single crystal X‐ray diffraction as well as thermogravimetric analysis. In the crystal structures of 1–4 and 5⋅CH2Cl2, the nickel atom locates in a slightly distorted square‐planar coordination by one phosphorous atom and three sulfur atoms from the aminodiphosphine monodulfide and O‐meyldithiophosphate ligands. Furthermore, their electrochemical behaviors and electrocatalytic performances for the reduction proton to hydrogen have also been evaluated by the cyclic voltammetry using trifluoroacetic acid (TFA) as the proton source. With the addition of 120 mM TFA to MeCN solution of 1–5 (1.0 mM), the turnover frequencies are estimated to be 494–706 s−1, and the corresponding overpotentials are 0.61–0.70 V versus Fc+/Fc, respectively. This finding diagnoses that the heteroleptic nickel complexes can serve as robust and effective molecular electrocatalysts for hydrogen evolution.

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Nickel Complexes Based on Thiophosphorylated Calix[4]Resorcinols as Effective Catalysts for Hydrogen Evolution

Cited by 19 publications

References 57 publications

Electrocatalytic Hydrogen Evolution Catalyzed by 3,4‐Toluenedithiolate Nickel Complexes of Bis(diphenylphosphine)amine Ligand Containing An Azahydrophilic Group

Electrocatalytic Hydrogen Evolution Catalyzed by 3,4‐Toluenedithiolate Nickel Complexes of Bis(diphenylphosphine)amine Ligand Containing An Azahydrophilic Group

Nickel Complexes of Pyridine‐Functionalized N‐Heterocyclic Carbenes: Syntheses, Structures, and Activity in Electrocatalytic Hydrogen Production

Heteroleptic nickel complexes bearing O‐methyldithiophosphate and aminodiphosphine monosulfide ligands as robust molecular electrocatalysts for hydrogen evolution

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