Hydrogen production from water using a bis(imino)pyridine molybdenum electrocatalyst

Abstract

Reduction of [(Ph2PPrPDI)MoO][PF6]2 affords an unusual Mo(ii) oxo compound that mediates the electrocatalytic reduction of water.

Hydrogen Evolution Reactions Catalyzed by a Bis(thiosemicarbazone) Cobalt Complex: An Experimental and Theoretical Study

“…During the last decade as pecial effort has been made in the field of renewable energy storagefor the design of new molecular catalytic systems [1][2][3][4][5] for the hydrogen evolutionr eaction (HER). The most efficient molecular catalysts are currently based on first-row transitionm etal ions like cobalt [6][7][8][9][10] and nickel.…”

Influence of the Metal Ion on the Electrocatalytic Hydrogen Production by a Thiosemicarbazone Palladium Complex

“…In the context of continued growth in energy demand, hydrogen can be a pertinent energy vector . Over the time, significant effort has been made in the field of renewable energy storage to design new molecular catalytic systems by focusing onto the synthesis of transition metal complexes active for electrocatalytic proton reduction . This approach was proven to be a good alternative to the classical method used for hydrogen production based on scarce and expensive platinum catalyst .…”

“…Transition metal complexes with bis(thiosemicarbazone) ligands have been studied for many years and are now emerging as a new class of electrocatalyst for HER catalysts , . These complexes present some interesting features that are relevant for electrocatalytic proton reduction: the thiosemicarbazone ligand has already been shown to be redox active while the presence of S‐donors and several N‐atoms allows protonation of the ligand , . In this context, we report here on the synthesis and the characterization of a bis(thiosemicarbazone) palladium complex that was evaluated as electrocatalyst for hydrogen evolution.…”

Synthesis, Structure, and Bonding of d3 Molybdenum–Oxo Complexes

“…Comparisons with Other Compounds . The structure and bonding of 5 may be compared with those for the metal–oxo complexes [Li(THF) 3 ][MoO(pyS 4 )] (pyS 4 H 2 =2,6‐bis(2‐mercaptophenylthio)dimethylpyridine), i Pr 3 TACN)MoO(OH)(NO) ( i Pr 3 TACN=1,4,7‐ i Pr 3 ‐1,4,7‐triazacyclononane), and MoO(PDI Ph2PPr ) (PDI Ph2PPr =2,6‐{(C 6 H 5 ) 2 PCH 2 CH 2 CH 2 N=C(CH 3 )} 2 C 5 H 3 N), which are the only three isolated molybdenum–oxo complexes that possess formal electron counts greater than d 2 . All three compounds possess features that complicate the interpretation of their metal oxidation states and comparisons to 5 .…”

“…Compared to 5 , the Mo−O bond length of ( i Pr 3 TACN)MoO(OH)(NO) is slightly shorter and the Mo−O stretching frequency is higher ( 5 /( i Pr 3 TACN)MoO(OH)(NO): d (MoO), 1.809(5)/1.775(5) Å; ν(MoO), 792/813 cm −1 ). The diamagnetic compound MoO(PDI Ph2PPr ), which was prepared by the two‐electron reduction of d 2 [MoO(PDI Ph2PPr )] 2+ , was described as having a Mo II oxidation state (d 4 ) and a formal Mo−O double bond . Interestingly, the MoO bond length of this reported d 4 compound (1.797(3) Å) is also similar to that of d 3 5 (1.809(5) Å), and is elongated by less relative to d 2 [MoO(PDI Ph2PPr )] 2+ (Δ d =0.104 Å) than is d 3 5 from d 2 5 + (Δ d =0.147 Å).…”