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Dalton Trans. 2013 Dec 7;42(45):15927-30. doi: 10.1039/c3dt51485d. Epub 2013 Sep 13.

Oxo-carboxylato-molybdenum(VI) complexes possessing dithiolene ligands related to the active site of type II DMSOR family molybdoenzymes.

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  • 1Department of Material and Life Science, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan. sugimoto@mls.eng.osaka-u.ac.jp shinobu@mls.eng.osaka-u.ac.jp.

Abstract

Spectroscopic and kinetic studies indicate that oxo-carboxylato-molybdenum(VI) bis-dithiolene complexes, (Mo(VI)O(p-X-OBz)L2), have been generated at low temperature as active site structural models for the type II class of pyranopterin molybdenum DMSOR family enzymes. A DFT analysis of low energy charge transfer bands shows that these complexes possess a Mo-S(dithiolene) π-bonding interaction between the Mo(d(xy)) redox active molecular orbital and a cis S(p(z)) donor orbital located on one of the dithiolene ligands.

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