Investigation of metal-dithiolate fold angle effects: Implications for molybdenum and tungsten enzymes

Hemant K. Joshi, J. Jon A. Cooney, Frank E. Inscore, Nadine E. Gruhn, Dennis L. Lichtenberger, John H. Enemark

Research output: Contribution to journalArticlepeer-review

83 Scopus citations


Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the interactions between the sulfur π-orbitals of arene dithiolates and high-valent transition metals as minimum molecular models of the active site features of pyranopterin Mo/W enzymes. The compounds (Tp*)MoO(bdt) (compound 1), Cp2Mo(bdt) (compound 2), and Cp2Ti(bdt) (compound 3) [where Tp* is hydrotris(3,5-dimethyl-1pyrazolyl)borate, bdt is 1,2-benzenedithiolate, and Cp is η5cyclopentadienyl] provide access to three different electronic configurations of the metal, formally d1, d2, and d0, respectively. The gas-phase photoelectron spectra show that ionizations from occupied metal and sulfur based valence orbitals are more clearly observed in compounds 2 and 3 than in compound 1. The observed ionization energies and characters compare very well with those calculated by density functional theory. A "dithiolate-folding-effect" involving an interaction of the metal in-plane and sulfur-π orbitals is proposed to be a factor in the electron transfer reactions that regenerate the active sites of molybdenum and tungsten enzymes.

Original languageEnglish (US)
Pages (from-to)3719-3724
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number7
StatePublished - Apr 1 2003

ASJC Scopus subject areas

  • General


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