Tungsten imido complexes bearing a redox-active ligand, such as N,N'-bis(2,6-dlisopropylphenyl)-1,4-diaza-2,3-dimethyl-1,3-butadiene (L1), N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (L2), and 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (L3), were prepared by salt-free reduction of W(=NC6H3-2,6-Pr-i(2))Cl-4 (1) using 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (MBTCD) followed by addition of the corresponding redox-active ligands. In the initial stage, reaction of W(=NC6H3-2,6-Pr-i(2))Cl-4. with MBTCD afforded a tetranuclear W(V) imido cluster, [W(=-NC6H3-2,6-Pr-i(2))Cl-3](4) (2), which served as a unique precursor for introducing redox-active ligands to the tungsten center to give the corresponding mononuclear complexes with a general formula of W(--=-NC6H3-2,6-Pr-i(2))Cl-3(L) (3, L = L1; 4, L = L2; and 6, L = L3). X-ray analyses of complexes 3 and 6 revealed a neutral coordination mode of Ll and L3 to the tungsten in solid state, while the electron paramagnetic resonance (EPR) spectra of 3 and 4 clarified that a radical was predominantly located on the tungsten center supported by neutral L1 or L2, and the EPR spectra of complex 6 indicated that a radical was delocalized over both the tungsten center and the monoanionic redox-active ligand L3.