Figure shows a solution spectrum recorded at -196 °C in frozen SO2. It reflects essentially axial symmetry with a considerable degree of isotropy for the g values. Couplings of 25  10 -4 cm -1 and 65  10 -4 cm -1 are due to the interaction of the unpaired electron with the nuclear spin of 183 W (I = ½, natural abundance: 14.3%). General features of the spectrum of [W(CNMe)8] 5+ well resemble with the spectral parameters derived for the octacyanotungstate(V) anion (see Supporting Information). The line widths are relatively broad and prevent the resolution of further couplings, particularly such of the Information regarding the X-Ray structures of the single crystals, IR/Raman, NMR, EPR spectroscopy as well as the DFT calculations can be found in the supporting information free of charge.