The synthesis, molecular and electronic structure of cyanovinylidene complexes

► The expeditious synthesis of novel cyanovinylidene complexes is described. ► The complexes have been crystallographically and (spectro)electrochemically characterised. ► DFT studies demonstrate a Cα-localised LUMO, consistent with experimental results. ► Improvements to the preparative routes of FeCl(dppe)Cp and 1-cyano-4-dimethylaminopyridinium tetrafluoroborate are described.