Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)₂]Cl [R = Me (1a), Et (1b)] (dppe = Ph₂PCH₂CH₂PPh₂) with HBF₄, [Et₃O][BF₄] or EtC(O)Cl gives trans-[Mo(NCN)Cl(dppe)₂]X [X = BF₄ (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R′)C(O)Et (R′ = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF₄) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)₂(dppe)₂] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans-[Mo(NCN)₂(dppe)₂], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.