The history of the cyaphide anion and all literature known preparations are reviewed. Furthermore, new theoretical insights to the cyaphide ion are presented and complemented with additional calculations. Moreover, several novel cyaphido complexes synthesized by two innovative preparation protocols are demonstrated. The first method takes advantage of a light induced C(sp2)-C(sp) cleavage reaction in a platinum(0) coordinated arylphosphaalkyne to generate the cyaphido ligand. The second method introduces the well-known trimethylsilylphosphaalkyne as cyaphide anion transfer reagent by fluorodesilylation to build new cyaphido gold(I) complexes. Finally, the reactivity of the cyaphido complexes were investigated towards consecutive reactions on the cyaphido moiety, especially by means of [3+2] cycloaddition reactions with organic azides to yield the corresponding triazaphospholato complexes.
