Inorganic Chemistry, Vol.48, No.13, 5829-5847, 2009
Electronic Structure of the [Tris(dithiolene)chromium](z)(z=0, 1-, 2-, 3-) Electron Transfer Series and Their Manganese(IV) Analogues. An X-ray Absorption Spectroscopic and Density Functional Theoretical Study
Three members of the electron transfer series [Cr-III(dithiolene)(3)](z) (z = 1-, 2-, 3-) along with [Mn-IV(dithiolene)(3)](2-) analogues are shown to possess Cr(III) and Mn(IV) ions, respectively, by X-ray absorption spectroscopy (Cr and Mn K-edges). S K-edge spectra show the Cr series to be linked by ligand-based redox processes. All complexes are octahedral with DFT calculations reproducing the molecular structures and spectroscopic parameters such that [Cr(dithiolene)(3)](0) is predicted to be and octahedral with three S,S'-coordinated radical ligands.