The reaction of cis-[Mo-2(O2C-Fc)(2)(NCCH3)(4)][BF4](2) (cis-1) with three electronically different N,N'-diarylformamidinate (DArF) ligands [DArF = N,N'-diphenylformamidinate (DPhF), N,N'-di(p-trifluoromethylphenyl)formamidinate (DTfmpF), and N,N'-di(p-anisyl)formamidinate (DAniF)] results in products of the general composition [Mo-2(O2C-Fc)(2)(DArF)(2)]. Even though the trans-[Mo-2(O2C-Fc)2(DArF)(2)] isomers were originally expected to be the sole products, the corresponding cis[Mo-2(O2C-Fc)(2)(DArF)(2)] complexes were isolated as well via crystallization and verified unambiguously by X-ray crystallography. All novel complexes, namely, cis-[Mo-2(O2C-Fc)(2)(DPhF)(2)] (cis-2a), cis-[Mo-2(O2C-Fc)(2)(DTfmpF)(2)] (cis-2b), and trans[Mo-2(O2C-Fc)(2)(DAniF)(2)] (trans-2c), were studied regarding their electrochemical properties with respect to electrolyte, solvent, and ligand. The electron-donating ligand DArF- enables the oxidation of the [Mo-2](4+) unit prior to that of Fc, while the oxidation sequence is reversed when acetonitrile or diphosphine ligands are coordinated instead of formamidinate. In the case of trans-[Mo-2(O2C-Fc)(2)(DAniF)(2)], interactions were found between the two redox-active ferrocenecarboxylate ligands, with a clear Delta E-1/2 value originating from the peak-to-peak separation in DPV of around 100 mV with CH2Cl2 as solvent. Furthermore, the second oxidation of the Mo-2-handle [Mo-2](5+)[Mo-2](6+) was exclusively observed with DAniF(-) as the ligand. Similar absorption patterns in UV-vis spectra were found within the series 2a-2c, corresponding to similar structural and electronic features of the complexes.