Photoelectron spectroscopy and electronic structure calculations of d 1 vanadocene compounds with chelated dithiolate ligands: Implications for pyranopterin Mo/W enzymes

Matthew A. Cranswick, Alice Dawson, J. Jon A. Cooney, Nadine E. Gruhn, Dennis L. Lichtenberger, John H. Enemark

Research output: Contribution to journalArticle

29 Scopus citations

Abstract

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the electronic structures of open-shell bent vanadocene compounds with chelating dithiolate ligands, which are minimum molecular models of the active sites of pyranopterin Mo/W enzymes. The compounds Cp 2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S 2C2H2) or 1,2-benzenedithiolate (bdt), and Cp is cyclopentadienyl] provide access to a 17-electron, d1 electron configuration at the metal center. Comparison with previously studied Cp 2M(dithiolate) complexes, where M is Ti and Mo (respectively d 0 and d2 electron configurations), allows evaluation of d0, d1, and d2 electronic configurations of the metal center that are analogues for the metal oxidation states present throughout the catalytic cycle of these enzymes. A "dithiolate-folding effect" that involves an interaction between the vanadium d orbitals and sulfur p orbitals is shown to stabilize the d1 metal center, allowing the d1 electron configuration and geometry to act as a low-energy electron pathway intermediate between the d0 and d2 electron configurations of the enzyme.

Original languageEnglish (US)
Pages (from-to)10639-10646
Number of pages8
JournalInorganic Chemistry
Volume46
Issue number25
DOIs
StatePublished - Dec 10 2007

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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