Interplay between terminal and bridging diiron hydrides in neutral and oxidized states

This study describes the structural, spectroscopic, and electrochemical properties of electronically unsymmetrical diiron hydrides. The terminal hydride Cp∗Fe(pdt)Fe(dppe)(CO)H ([1(t-H)]⁰, Cp∗^- = Me₅C₅^-, pdt^2- = CH₂(CH₂S^-)₂, dppe = Ph₂PC₂H₄PPh₂) was prepared by hydride reduction of [Cp∗Fe(pdt)Fe(dppe)(CO)(NCMe)]⁺. As established by X-ray crystallography, [1(t-H)]⁰ features a terminal hydride ligand. Unlike previous examples of terminal diiron hydrides, [1(t-H)]⁰ does not isomerize to the bridging hydride [1(μ-H)]⁰. Oxidation of [1(t-H)]⁰ gives [1(t-H)]⁺, which was also characterized crystallographically as its BF₄^- salt. Density functional theory (DFT) calculations indicate that [1(t-H)]⁺ is best described as containing an Cp∗Fe^III center. In solution, [1(t-H)]⁺ isomerizes to [1(μ-H)]⁺, as anticipated by DFT. Reduction of [1(μ-H)]⁺ by Cp₂Co afforded the diferrous bridging hydride [1(μ-H)]⁰. Electrochemical measurements and DFT calculations indicate that the couples [1(t-H)]^+/0 and [1(μ-H)]^+/0 differ by 210 mV. Qualitative measurements indicate that [1(t-H)]⁰ and [1(μ-H)]⁰ are close in free energy. Protonation of [1(t-H)]⁰ in MeCN solution affords H₂ even with weak acids via hydride transfer. In contrast, protonation of [1(μ-H)]⁰ yields 0.5 equiv of H₂ by a proposed protonation-induced electron transfer process. Isotopic labeling indicates that μ-H/D ligands are inert.