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Updated: Jun 23, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Isolation of Mo(V)-dithiolene-radical: an elusive intermediate species relevant to catalytic cycle of molybdenum
Sujit Das1, Harsha S Karnamkkott1, Ashitha Kolothumthodi1
1Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036, India. csdkartik@iitm.ac.in.
Abstract:
A pair of bis-dithiolene-molybdenum(V) complexes, [Mo(V)(O)(LE2-)(LE˙-)] [E = S (1), E = Se (2), LE = NHC-based dithiolene ligand] have been successfully isolated and fully characterised. These complexes represent a rare and well-defined structural analogue of the active sites found in molybdenum cofactor enzymes (Moco) in bacteria. They were spectroscopically characterised with IR, UV-Vis, XPS, and EPR measurements. Stability, bonding and distribution of electron densities were studied by DFT and EDA-NOCV calculations. Notably, this work constitutes the first report of a molybdenum-oxo bisdithiolene complex in which the same ligand simultaneously exists [C-C 1.411(6), 1.350(6) Å] in radical monoanionic and closed-shell dianionic forms, which was previously speculated.
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