Photoluminescent Mo(IV) and W(IV) bis-dithiolene complexes with bidentate phosphonodithioato ligand derived from Lawesson's reagent

Synthesis of phosphonodithioato complexes of Mo(IV) and W(IV) bis- dithiolene have been reported. These complexes are characterized by elemental analysis, X-ray crystallography, IR, UV-Vis, P-31 NMR, and photoluminescence spectroscopy, electrochemical studies and these results are corroborated by DFT level of calculations. Phosphonodithioato ligands is generated in situ from the reaction of Lawesson's reagent with mono-oxo Mo/W bis dithiolenes complexes resulting its chelation coupled with oxo transfer reaction from M(IV) bound oxo to {P=S} moiety forming (P=O} group. The new complexes are photoluminescent at room temperature. (C) 2012 Elsevier Ltd. All rights reserved.