Amido rotation in the chromium(VI), d0-system NCr(NPri2)2X is under investigation as a method for the parameterization of ligands for their donor properties toward high valent metals. In this study, two new series were prepared and studied based on chalcogenide ligands, X = EBut and EPh and where E = O, S, Se, Te; the OPh and SPh compounds were previously reported. The ligand donor parameters for these ligands correlate with the Cr–E–C angles in these chalcogenide series. In addition, it was found that NBO calculated overlaps and DFT calculated bond dissociation enthalpies correlate within X = halide-, EBut- and EPh-series. All of the new complexes were characterized by X-ray diffraction.