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A series of new diiron hydrogenase mimic complexes with one or two terminal tris(4\u2010methoxyphenyl)phosphine and different \u03bc\u2010bridging dithiolate ligands and show catalytic activity towards electrochemical proton reduction in the presence of weak and strong acids. A series of propane\u2010 and benzene\u2010dithiolato\u2010bridged complexes was synthesized, crystallized, and characterized by various spectroscopic techniques and quantum chemical calculations. Their electrochemical properties as well as the detailed reaction mechanisms of the HER are elucidated by density functional theory (DFT) methods. The nature of the \u03bc\u2010bridging dithiolate is critically controlling the reaction and performance of the HER of the complexes. In contrast, terminal phosphine ligands have no significant effects on redox activities and mechanism. Mono\u2010 or di\u2010substituted propane\u2010dithiolate complexes afford a sequential reduction (electrochemical; E) and protonation (chemical; C) mechanism (ECEC), while the \u03bc\u2010benzene dithiolate complexes follow a different reaction mechanism and are more efficient HER catalysts.<\/jats:p>","DOI":"10.1002\/open.202100238","type":"journal-article","created":{"date-parts":[[2022,1,4]],"date-time":"2022-01-04T06:49:07Z","timestamp":1641278947000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Mechanism of Diiron Hydrogenase Complexes Controlled by Nature of Bridging Dithiolate Ligand"],"prefix":"10.1002","volume":"11","author":[{"given":"Mookan","family":"Natarajan","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Delhi  Delhi 110007 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