A Novel [FeFe] Hydrogenase Model with a (SCH<sub>2</sub>)<sub>2</sub>PO Moiety
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A novel [FeFe]-hydrogenase model complex containing phosphine oxide in the dithiolato ligand, namely [Fe2(CO)6][(μ-SCH2)2(Ph)PO] (1), has been synthesized and characterized. Complex 1 was prepared via the reaction of equimolar quantities of (μ-LiS)2Fe2(CO)6 and OP(Ph)(CH2Cl)2. The protonation properties of complex 1 have been investigated by monitoring the changes in IR (in the ν(CO) region) and 31P{1H} NMR spectra upon addition of pyridinium tetrafluoroborate, [HPy][BF4], and HBF4·Et2O, suggesting protonation of the PO functionality. In addition, high-level DFT calculations on the protonation sites of complex 1 in CH2Cl2 have been performed and support our experimental observations that the PO unit is protonated by HBF4·Et2O. Cyclic voltammetric experiments on complex 1 showed an anodic shift of the oxidation peak upon addition of HBF4·Et2O, suggesting a CE process.
