Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM
Abstract
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 × 10 3 s ‐1 , an overpotential of 0.56 V, and faradaic efficiency of 100 %.
- Publication Date:
- Research Org.:
- Univ. of Louisville, KY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1609952
- Alternate Identifier(s):
- OSTI ID: 1558811
- Grant/Contract Number:
- FG02-08CH11538; DEFG02‐08CH11538
- Resource Type:
- Accepted Manuscript
- Journal Name:
- European Journal of Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 2019; Journal Issue: 33; Journal ID: ISSN 1434-1948
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Calvary, Caleb A., Hietsoi, Oleksandr, Strain, Jacob M., Mashuta, Mark S., Spurgeon, Joshua M., Buchanan, Robert M., and Grapperhaus, Craig A. Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM. United States: N. p., 2019.
Web. doi:10.1002/ejic.201900721.
Calvary, Caleb A., Hietsoi, Oleksandr, Strain, Jacob M., Mashuta, Mark S., Spurgeon, Joshua M., Buchanan, Robert M., & Grapperhaus, Craig A. Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM. United States. https://doi.org/10.1002/ejic.201900721
Calvary, Caleb A., Hietsoi, Oleksandr, Strain, Jacob M., Mashuta, Mark S., Spurgeon, Joshua M., Buchanan, Robert M., and Grapperhaus, Craig A. Mon .
"Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM". United States. https://doi.org/10.1002/ejic.201900721. https://www.osti.gov/servlets/purl/1609952.
@article{osti_1609952,
title = {Synthesis, Characterization, and HER Activity of Pendant Diamine Derivatives of NiATSM},
author = {Calvary, Caleb A. and Hietsoi, Oleksandr and Strain, Jacob M. and Mashuta, Mark S. and Spurgeon, Joshua M. and Buchanan, Robert M. and Grapperhaus, Craig A.},
abstractNote = {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 × 10 3 s ‐1 , an overpotential of 0.56 V, and faradaic efficiency of 100 %.},
doi = {10.1002/ejic.201900721},
journal = {European Journal of Inorganic Chemistry},
number = 33,
volume = 2019,
place = {United States},
year = {Mon Aug 12 00:00:00 EDT 2019},
month = {Mon Aug 12 00:00:00 EDT 2019}
}
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