TY - JOUR
TI - Structural modifications on nickel dithiolene complexes lead to increased metal participation in the electrocatalytic hydrogen evolution mechanism
AU - Drosou, M.
AU - Zarkadoulas, A.
AU - Bethanis, K.
AU - Mitsopoulou, C.A.
JO - Journal of Coordination Chemistry
PY - 2021
VL - 74
TODO - 9-10
SP - 1425-1442
PB - Taylor and Francis Ltd.
SN - 0095-8972, 1029-0389
TODO - 10.1080/00958972.2021.1918339
TODO - null
TODO - In this work we present the electrocatalytic activity of alkylated nickel bis-dithiolene complexes toward hydrogen evolution from protons (TFA) in organic media (DMF). The hydrogen evolving mechanism is discussed and the complexes are compared to their non-alkylated analogs using DFT calculations. The findings support increased metal participation in the hydrogen evolving mechanism due to the structural and electronic modifications imposed by the alkyl-bridge on the sulfur atoms. Typically for this class of compounds, the coordinated sulfur atoms act as internal proton relays that facilitate transfer of protons to the metal ion during the catalytic cycle, highlighting the importance of modifying the coordination sphere of metal ions in the design of homogeneous hydrogen evolving catalysts. © 2021 Informa UK Limited, trading as Taylor & Francis Group.
ER -