Low-valent molybdenum dicarbonyl complexes with a diazabutadiene [(mes)DAB(R); [ArN═C(R)C(R)═NAr]; Ar = 2,4,6-trimethylphenyl (mes), R = H or CH3] ligand have been synthesized and fully characterized. The title complexes exhibit elongated DAB C-N and shortened C-C bond lengths over the free ligand and other zerovalent molybdenum complexes of DAB. Compared to known examples theoretically described as iminato π-radicals (L(•-)), the oxidation state assignment fits a molybdenum(II) description. However, Mo K-edge X-ray absorption spectroscopy indicates that the complexes are best described as molybdenum(0). This example demonstrates that caution should be exercised in assigning the oxidation state based on structural parameters alone. Cyclic voltammetry studies reveal an electrochemical-chemical process that has been identified by in situ Fourier transform infrared spectroelectrochemistry as cis-to-trans isomerization.