Document Type
Article
Version
Final Published Version
Publication Title
Inorganic Chemistry
Volume
38
Publication Date
1999
Abstract
The synthesis and structure of a new molybdenum complex coordinated by a reduced pterin is reported. [MoOCl(detc)(H3dmp)]Cl (1) (where detc is diethyldithiocarbamate and H3dmp is 6,7-dimethyl-6,7,8-trihydropterin) is prepared from MoOCl2(detc)2 and H4dmp (6,7-dimethyl-5,6,7,8-tetrahydropterin). The X-ray structure determination of [MoOCl(detc)(H3dmp)]Cl·MeOH reveals an octahedral complex where the reduced pterin ligand coordinates through the carbonyl oxygen and pyrazine ring nitrogen atoms. An extensive hydrogen bonding network in the crystal lattice connects adjacent complexes, the chloride counterion, and the molecule of methanol. This hydrogen bonding persists in solution where it is identified by characteristic absorptions in the electronic spectrum. Dimethyl sulfoxide (DMSO) oxidizes [MoOCl(detc)(H3dmp)]Cl, producing 1 equiv of dimethylpterin and 1/2 equiv of oxidized dithiocarbamate, tetraethylthiuramdisulfide (TETDS), a reaction that constitutes a net five-electron oxidation of the molybdenum complex 1. Pterin oxidation is also observed for 1 in dimethylformamide (DMF) solution where it is believed to result from intermolecular electron transfer mediated by the hydrogen-bonding network.
Citation
Kaufmann, Heather Layton, Louise Liable-Sands, Arnold L. Rheingold, and Sharon J. Nieter Burgmayer. 1999. “Molybdenum−Pterin Chemistry. 1. The Five-Electron Oxidation of an Oxo Molybdenum Dithiolate Complex of a Reduced Pterin.” Inorganic Chemistry 38 (11): 2592–99. https://doi.org/10.1021/ic980881z.
DOI
https://doi.org/10.1021/ic980881z