Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes.

Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes. Research Abstract Details 

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Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes. Abstract Text:

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

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 Cp2V(dithiolate) [where dithiolate is 1,2-ethenedithiolate (S2C2H2) 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 Cp2M(dithiolate) complexes, where M is Ti and Mo (respectively d0 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.

Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes. Publishing Authors By Initials

MA Cranswick,A Dawson,JJ Cooney,NE Gruhn,DL Lichtenberger,JH Enemark,MA Cranswick,A Dawson,JJ Cooney,NE Gruhn,DL Lichtenberger,JH Enemark,MA Cranswick,A Dawson,JJ Cooney,NE Gruhn,DL Lichtenberger,JH Enemark,

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Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Inorganic chemistry

VOLUME: 46

Page Numbers: 10639-46

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ISSN: 0020-1669

DAY: 15

MONTH: 11

YEAR: 2007

Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes. Information

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LANGUAGE: eng

NlmUniqueID: 366543

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Grant and Affiliation Information for Photoelectron spectroscopy and electronic structure calculations of d1 vanadocene compounds with chelated dithiolate ligands: implications for pyranopterin Mo/W enzymes.

AFFILIATION: Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM-37773

ACRONYM: GM

MEDLINETA: Inorg Chem

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