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

Xin Yu, Chen Ho Tung, Wenguang Wang, Mioy T. Huynh, Danielle L. Gray, Sharon Hammes-Schiffer, Thomas B. Rauchfuss

Research output: Contribution to journalArticlepeer-review

25 Scopus citations


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-, pdt2- = 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∗FeIII 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.

Original languageEnglish (US)
Pages (from-to)2245-2253
Number of pages9
Issue number11
StatePublished - Jun 12 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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