Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM

Calvary, Caleb A.; Hietsoi, Oleksandr; Strain, Jacob M.; Mashuta, Mark S.; Spurgeon, Joshua M.; Buchanan, Robert M.; Grapperhaus, Craig A.

doi:10.1002/ejic.201900721

Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM

Journal Article · Mon Aug 12 00:00:00 EDT 2019 · European Journal of Inorganic Chemistry

DOI:https://doi.org/10.1002/ejic.201900721· OSTI ID:1609952

^[1]; ^[2]; ^[2]; Mashuta, Mark S. ^[2]; Spurgeon, Joshua M. ^[2]; ^[2]; ^[2]

Univ. of Louisville, KY (United States); DOE/OSTI
Univ. of Louisville, KY (United States)

A pair of bis-thiosemicarbazonato-Ni(II) complexes with pendant polyamines, (N,N'-(dimethylethylenediaminothiosemi-carbazonato)-4-(methylthiosemi-carbazonato)butane-2,3-diimine)-nickel(II) (1) and (N,N'-bis(dimethylethyl-enediaminothiosemi-carbazonato)butane-2,3-diimine)-nickel(II) (3), have been synthesized. Methylation at the terminal amines yields the cationic derivatives 2 and 4. All complexes are fully characterized by spectroscopic, electrochemical, and single-crystal X-ray diffraction methods. Single crystal X-ray diffraction studies on all four Ni(II) complexes confirm a square planar Ni(II) framework with no significant changes in the coordination environment as a function of the pendant groups. Spectroscopic studies are consistent with a similar electronic structure in all complexes. However, electrochemical investigations reveal significant cathodic shifts in the Ni(II)L/Ni(II)L^·– and Ni(II)L^·–/Ni(I)L^·2– reduction potentials of the methylated vs. non-methylated species. The HER activity of all four nickel complexes were evaluated in acetonitrile with glacial acetic acid. The 3 complex was shown to have the highest activity with a TOF of 6.3 × 10³ s^-1, an overpotential of 0.56 V, and faradaic efficiency of 100%.

View Accepted Manuscript (DOE)

Research Organization:: University of Louisville, KY (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC)

Grant/Contract Number:: FG02-08CH11538

OSTI ID:: 1609952

Alternate ID(s):: OSTI ID: 1558811

Journal Information:: European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 33 Vol. 2019; ISSN 1434-1948

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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