A reduced 2Fe2S cluster probe of sulfur-hydrogen versus sulfur-gold interactions. Academic Article uri icon


  • The Ph3 PAu(+) cation, renowned as an isolobal analogue of H(+) , was found to serve as a proton surrogate and form a stable Au2 Fe2 complex, [(-SAuPPh3 )2 {Fe(CO)3 }2 ], analogous to the highly reactive dihydrosulfide [(-SH)2 {Fe(CO)3 }2 ]. Solid-state X-ray diffraction analysis found the two SAuPPh3 and SH bridges in anti configurations. VT NMR studies, supported by DFT computations, confirmed substantial barriers of approximately 25kcalmol(-1) to intramolecular interconversion between the three stereoisomers of [(-SH)2 {Fe(CO)3 }2 ]. In contrast, the largely dative SAu bond in -SAuPPh3 facilitates inversion at S and accounts for the facile equilibration of the SAuPPh3 units, with an energy barrier half that of the SH analogue. The reactivity of the gold-protected sulfur atoms of [(-SAuPPh3 )2 {Fe(CO)3 }2 ] was accessed by release of the gold ligand with a strong acid to generate the [(-SH)2 {Fe(CO)3 }2 ] precursor of the [FeFe]H2 ase-active-site biomimetic [(2 -SCH2 (NR)CH2 S){Fe(CO)3 }2 ].

published proceedings

  • Angew Chem Int Ed Engl

altmetric score

  • 0.25

author list (cited authors)

  • Crouthers, D. J., Ding, S., Denny, J. A., Bethel, R. D., Hsieh, C., Hall, M. B., & Darensbourg, M. Y.

citation count

  • 9

complete list of authors

  • Crouthers, Danielle J||Ding, Shengda||Denny, Jason A||Bethel, Ryan D||Hsieh, Chung-Hung||Hall, Michael B||Darensbourg, Marcetta Y

publication date

  • September 2015