Sulphur-sulphur, sulphur-selenium, selenium-selenium and selenium-carbon bond activation using Fe3(CO)12: an unexpected formation of an Fe2(CO)6 complex containing a μ2,κ3-C,O,Se-ligand

Three diiron hexacarbonyl complexes containing dithiolato (5), diselenolato (6), and selenolato-thiolato ligands (7), respectively, have been prepared as [FeFe]-hydrogenase mimics. Treatment of Fe-3(CO)(12) with one equivalent of the corresponding 5-membered heterocycles 1, 3 and 4 in toluene at reflux afforded the corresponding complexes 5-7. The reaction of 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane with in situ generated Na2Se2 results in the formation of 8,8-dimethyl-7,9-dioxa-2,3-diselenaspiro[4.5]decane (1) and traces of 7,7-dimethyl-6,8-dioxa-2-selenaspiro[3.4]nonane (2). Alternatively, 5,5-bis(bromomethyl)-2,2-dimethyl-1,3-dioxane reacts with in situ generated Na2Se yielding compound 2 in 26% yield. When Fe-3(CO)(12) reacts under reflux with the selenaspiro compound 2 in toluene, the unique diiron complex, [Fe-2(CO)(6){mu(2),kappa(3)-Se,C,O-SeCH2C7H12O2}] (8), is obtained as a result of an initial selenium-carbon bond activation. Compounds 5, 6, 7, and 8 were characterized by IR, H-1, C-13{H-1}, and Se-77{H-1} NMR spectroscopy, mass spectrometry, elemental analysis, and X-ray single-crystal structure analysis. The chiral complex 8 shows a coordination of the O atom at the dioxane ring to one Fe atom and the O-CH- carbanionic group to the other Fe atom. Furthermore, we investigated the redox properties and the catalytic behaviour of complexes 5-8 in the presence of AcOH as a source of protons. The reduction of complexes 5-7 is accompanied by a chemical process resulting in an overall two-electron transfer at their primary reduction wave. This observation is consistent with an ECE reduction (E = electrochemical process, C = chemical process), while each reduction event in the case of complex 8 involves simple transfer of one electron. Moreover, high level DFT calculations were performed on neutral 8 and its reduction products 8(-) and 8(2-).