A series of novel neutral tungsten(III) and cationic tungsten(IV) complexes with disubstituted 4,4'-R,R-2,2'-bipyridyl (R-2-bpy) ligands of the type [Cp*W(R-2-bpy)Cl-2](n+) (n = 0,1) were prepared and chararacterized by X-ray crystallography. Susceptibility measurements of the tungsten(IV) complexes revealed an intrinsic paramagnetism of these compounds and evidenced different magnetic properties of the dimethylamino and methyl (R = NMe2, Me) substituted tungsten(IV) compounds in solution and in the solid state. In dichloromethane solution, singlet ground states with thermally populated triplet states were observed, whereas triplet (R = Me) and singlet ground states (R = NMe2) were observed in the solid state. Using both experimental and theoretical techniques (DFT) allowed to establish solvation and ligand effects to account for the different magnetic behavior. Thermodynamic parameters were derived for the spin equlibria in solution by fits of the temperature dependent H-1 NMR shifts to the Van Vleck equation and were found to be in excellent agreement with the DFT calculations.