Author's Final Manuscript
Journal of the American Chemical Society
The syntheses and X-ray structures of two molybdenum pyranopterin dithiolene complexes in biologically relevant Mo(+4) and Mo(+5) states are reported. Crystallography reveals these complexes possess a pyran ring formed through a spontaneous cyclization reaction of a dithiolene side-chain hydroxyl group at a C=N bond of the pterin. NMR data on the Mo(+4) complex suggests a reversible pyran ring cyclization occurs in solution. These results provide experimental evidence that the pyranopterin dithiolene ligand in molybdenum and tungsten enzymes could participate in catalysis through dynamic processes modulated by the protein.
This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work, see http://pubs.acs.org/doi/abs/10.1021/ja310018e
Benjamin R. Williams, Yichun Fu, Glenn P. A. Yap, and Sharon J. Nieter Burgmayer, "Structure and Reversible Pyran Formation in Molybdenum Pyranopterin Dithiolene Models of the Molybdenum Cofactor," J Am Chem Soc. 2012 Dec 5; 134(48): 19584–19587.