Cobalt, nickel, and iron complexes of 8-hydroxyquinoline-di(2-picolyl)amine for light-driven hydrogen evolution

2017 ◽  
Vol 46 (47) ◽  
pp. 16455-16464 ◽  
Author(s):  
Nadia Alessandra Carmo dos Santos ◽  
Mirco Natali ◽  
Elena Badetti ◽  
Klaus Wurst ◽  
Giulia Licini ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Hydrogen Evolution ◽  
Transition Metal Complexes ◽  
Iron Complexes ◽  
Cobalt Nickel ◽  
Amine Ligand

Novel first-row transition metal complexes based on the 8-hydroxyquinoline-di(2-picolyl)amine ligand were prepared and tested as potential HECs in light-driven experiments.

First-row transition metal porphyrins for electrocatalytic hydrogen evolution — a SPP/JPP Young Investigator Award paper

2020 ◽  
Vol 24 (11n12) ◽  
pp. 1361-1371
Author(s):  
Haitao Lei ◽  
Yabo Wang ◽  
Qingxin Zhang ◽  
Rui Cao
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Hydrogen Evolution ◽  
Transition Metal Complexes ◽  
Catalytic Efficiency ◽  
Electrochemical Analysis ◽  
Metal Porphyrin ◽  
High Turnover ◽  
Faradaic Efficiency ◽  
Metal Porphyrins

A series of first-row transition metal complexes of tetrakis(pentafluorophenyl)porphyrin (1), denoted as 1-M (M [Formula: see text] Mn, Fe, Co, Ni, Cu, and Zn), were synthesized and examined as electrocatalysts for the hydrogen evolution reaction (HER). All these transition metal porphyrins were shown to be active for HER in acetonitrile using trifluoroacetic acid (TFA) as the proton source. The molecular nature and the stability of these metal porphyrins when functioning as HER catalysts were confirmed, and all catalysts gave Faradaic efficiency of >97% for H2 generation during bulk electrolysis. Importantly, by using 1-Cu, a remarkably high turnover frequency (TOF) of 48500 s[Formula: see text] 1-Cu the most efficient among this series of metal porphyrin catalysts. This TOF value also represents one of the highest values reported in the literature. In addition, electrochemical analysis demonstrated that catalytic HER mechanisms with these 1-M complexes are different. These results show that with the same porphyrin ligand, the change of metal ions will have significant impact on both catalytic efficiency and mechanism. This work for the first time provides direct comparison of electrocatalytic HER features of transition metal complexes of tetrakis(pentafluorophenyl)porphyrin under identical conditions, and will be valuable for future design and development of more efficient HER electrocatalysts of this series.

scholarly journals Reaktive π-Komplexe der elektronenreichen Übergangsmetalle, 11. Mitteilung/ Reactive π-Complexes of the Electron Rich Transition Metal Complexes, Part 11

1991 ◽  
Vol 46 (6) ◽  
pp. 729-737 ◽  
Author(s):  
Catherine Tolxdorff ◽  
Dongqi Hu ◽  
Bernhard Höferth ◽  
Hartmut Schaufele ◽  
Hans Pritzkow ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Room Temperature ◽  
Iron Complexes ◽  
Iron Complex

The highly reactive arene iron complex [(η4-toluene)(η6-toluene)iron] allows the formation of C4-units from alkynes below room temperature. By this route butadiene-, cyclobutadiene-, and ferracyclopentadiene(arene)iron complexes are accessible. Synthesis, structure and the properties of one example each are reported. Ferracyclopentadienes are potential intermediates for the catalytic cyclotrimerization of alkynes in the coordination sphere of arene iron complexes.

scholarly journals Tandem redox mediator/Ni(ii) trihalide complex photocycle for hydrogen evolution from HCl

2015 ◽  
Vol 6 (2) ◽  
pp. 917-922 ◽  
Author(s):  
Seung Jun Hwang ◽  
David C. Powers ◽  
Andrew G. Maher ◽  
Daniel G. Nocera
Keyword(s):  
Excited State ◽  
Transition Metal ◽  
Metal Complexes ◽  
Hydrogen Evolution ◽  
Transition Metal Complexes ◽  
Redox Mediator ◽  
Metal Catalyst ◽  
Nickel Metal ◽  
Excited State Lifetimes

The challenge that short excited state lifetimes of first-row transition metal complexes present to the photoactivation of M–X bonds has been overcome with a phosphine mediator coupled to a nickel metal catalyst.

Übergangsmetallkomplexe mit Schwefelliganden, XCl+ Fell-Komplexe des fünfzähnigen Thioether-Thiolat-Aminliganden ′buNHS4′-H2: Synthese, Charakterisierung, Reaktivität und Stereochemie (′buNHS4′-H2 = 2,2′-Bis(2-mercapto-3,5-di-tertiärbutyl-phenylthio)diethylamin) / Transition Metal Complexes with Sulfur Ligands, XCI+ Fell Complexes of the Pentadentate Thioether-Thiolate-Amine Ligand ′buNHS4′-H2: Synthesis, Characterization, Reactivity and Stereochemistry (′buNHS4′-H2 = 2,2′-Bis(2-mercapto-3,5-di-tertiarybutyl-phenylthio)diethylamine)

1992 ◽  
Vol 47 (8) ◽  
pp. 1105-1114 ◽  
Author(s):  
Dieter Sellmann ◽  
Wolfgang Soglowek ◽  
Matthias Moll
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Low Temperatures ◽  
Positional Isomers ◽  
Model Compounds ◽  
Active Centers ◽  
High Spin Complex ◽  
Amine Ligand ◽  
Spin Complex

In search of model compounds for the active centers of nitrogenases, [Fe(L)(′buNHS4')] complexes of the pentadentate thioether-thiolate-amine ligand ′buNHS4'2- (′buNHS4'-H2 = 2,2′-bis(2-mercapto-3,5-di-tertiarybutyl-phenylthio)diethylamine) were obtained.Alkylation of′buS2'-H2 with (BrC2H4)2NH yielded the new ligand ′buNHS4'-H2 as a mixture of positional isomers. Isolation of single isomers was achieved by reacting the mixture with FecL2•4H2O and CO in order to give the corresponding [Fe(CO)] complexes which were separated and hydrolyzed to yield the free ligands.Reaction of'buNHS4'-H2 with FeCl2•4H2O led to the high-spin complex [Fe(′buNHS4')] which is extremely air-sensitive in solution. It rapidly reacts with L = CO, NO, PMe3, and N2H4, and is the most suitable starting material for syntheses of [Fe(L)(′buNHS4')] complexes which were characterized for L = CO, NO+, NO, PMe3 and N2H4. All complexes are considerably better soluble in organic solvents than the corresponding parent compounds [Fe(L)(′NHS4')], (′NHS4'-H2 = 2,2′-bis(2-mercaptophenylthio)diethylamine), but have similar properties in most other respects. In the oxidation of [Fe(N2H4)(′buNHS4')] at low temperatures, there is evidence for the formation of the diazene complex [μ-N2H2{Fe(′buNHS4')}2].

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