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

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) ?-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.

SUBMITTER: Sugimoto H

PROVIDER: S-EPMC3856207 | biostudies-literature | 2013 Dec

REPOSITORIES: biostudies-literature

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

Sugimoto Hideki H Sato Masanori M Giles Logan J LJ Asano Kaori K Suzuki Takeyuki T Kirk Martin L ML Itoh Shinobu S

Dalton transactions (Cambridge, England : 2003) 20130913 45

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 ...[more]

PMID: 24029827

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