@article{34174,
  author = {Andrew Z Haddad and Steve P Cronin and Mark S Mashuta and Robert M Buchanan and Craig A Grapperhaus},
  title = {Metal-Assisted Ligand-Centered Electrocatalytic Hydrogen Evolution upon Reduction of a Bis(thiosemicarbazonato)Cu(II) Complex},
  abstract = {<p><span>In this study, we report the electrocatalytic behavior of the neutral, monomeric Cu(II) complex of diacetyl-bis(</span><em>N</em><span>-4-methyl-3-thiosemicarbazonato), CuL</span><span>1</span><span>, for metal-assisted ligand-centered hydrogen evolution in acetonitrile and dimethylformamide. CuL</span><span>1</span><span>&nbsp;displays a maximum turnover frequency (TOF) of 10 000 s</span><span>–1</span><span>&nbsp;in acetonitrile and 5100 s</span><span>–1</span><span>&nbsp;in dimethylformamide at an overpotential of 0.80 and 0.76 V, respectively. The rate law is first-order in catalyst and second-order in proton concentration. Gas analysis from controlled potential electrolysis confirms CuL</span><span>1</span><span>&nbsp;as an electrocatalyst to produce H</span><span>2</span><span>&nbsp;with a minimum Faradaic efficiency of 81% and turnover numbers as high as 73 while showing no sign of degradation over 23 h. The H</span><span>2</span><span>&nbsp;evolution reaction (HER) was probed using deuterated acid, demonstrating a kinetic isotope effect of 7.54. A proton inventory study suggests one proton is involved in the rate-determining step. Catalytic intermediates were identified using&nbsp;</span><span>1</span><span>H NMR, X-ray photoelectron, and UV–visible spectroscopies. All catalytic intermediates in the proposed mechanism were successfully optimized using density functional theory calculations with the B3LYP functional and the 6-311g(d,p) basis set and support the proposed mechanism.</span></p>},
  year = {2017},
  journal = {Inorganic Chemistry},
  volume = {56},
  pages = {11254 - 11265},
  month = {08/2017},
  issn = {0020-1669},
  doi = {10.1021/acs.inorgchem.7b0160810.1021/acs.inorgchem.7b01608.s001},
  language = {eng},
}