Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates

Richard S. Glass, Nadine E. Gruhn, Edward Lorance, Maya S. Singh, Nhu Y.T. Stessman, Uzma I. Zakai

Research output: Contribution to journalArticle

17 Scopus citations

Abstract

Stannylated dinuclear iron dithiolates (μ-SSnMe2CH 2S)[Fe(CO)3]2, (μ-SCH2SnMe 2CH2S) [Fe(CO)3]2, and (μ-SCH2-SnMe3)2[Fe(CO)3] 2, which are structurally similar to the active site of iron-only hydrogenase, were synthesized and studied by gas-phase photoelectron spectroscopy. The orbital origins of ionizations were assigned by comparison of He I and He II photoelectron spectra and with the aid of hybrid density functional electronic structure calculations. Stannylation lowers the ionization energy of sulfur lone pair orbitals in these systems owing to a geometry-dependent interaction. The Fe-Fe σ bond, which is the HOMO in all these systems, is also substantially destabilized by stannylation due to a previously unrecognized geometry-dependent interaction between axial sulfur lone pair orbitals and the Fe-Fe σ bond. Since cleaving the Fe-Fe σ bond is a key step in the mechanism of action of iron-only hydrogenase, these newly recognized geometry-dependent interactions may be utilized in designing biologically inspired hydrogenase catalysts.

Original languageEnglish (US)
Pages (from-to)5728-5737
Number of pages10
JournalInorganic Chemistry
Volume44
Issue number16
DOIs
StatePublished - Aug 8 2005

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Synthesis, gas-phase photoelectron spectroscopic, and theoretical studies of stannylated dinuclear iron dithiolates'. Together they form a unique fingerprint.

  • Cite this