We have pursued an area of biomimetic chemistry where the role of thiolate-S bridges, and the possibility of assembling homo- and hetero-bimetallic complexes with core M(µ-SR)2M’ features of these sites, have guided synthetic efforts.1 Redox activity occurs within the active sites of the [FeFe]- and [NiFe]-H2ases, and at least with the former the added electrons are delocalized or stored over multiple metals, the two irons and the proximal, redox active, 4Fe4S cluster.2 In the [NiFe]-H2ase active site, (CysS)2Ni(µ-CysS)2FeII(CO)(CN)2, questions remain as to whether the bridging thiolates belong in covalent attachment to the iron or the nickel, i.e., which metal dithiolate fragment, if either, should be defined as a metallodithiolate ligand. A clearer delineation exists in the Acetyl coA Synthase, ACS, site where a square planar, redox innocent, NiN2S2 unit has been shown to readily take up copper, zinc, or nickel at the cis-dithiolates, with only the second nickel leading to catalytic activity. To address the possibility of covalent/coordinate-covalent switches between donor and acceptor bridging thiolate complexes, we describe properties of a set of bimetallic complexes, with redox activity varying in the combinations of innocent (redox inactive) or non-innocent acceptors with innocent or non-innocent (redox active) donors. -------- 1 Jason A. Denny, Marcetta Y. Darensbourg Chem. Rev. 2015, 115, 5248-5273. 2 Wolfgang Lubitz , Hideaki Ogata , Olaf Rüdiger , and Edward Reijerse, Chem. Rev. 2014, 114 , 4081–4148

Sulfur directed acid-base pairs as guiding principle for adjudicating guilt vs. innocence in heterobimetallic complexes derived from metallodithiolate ligands

251st National Meeting (2016)

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