A Monometallic Bis(cyaphido) Complex

The first example of a bis(cyaphido) complex, trans‐[Ru(dppe)2(CºP)2], is described, unequivocally demonstrating the synthetic accessibility and stability of complexes that feature more than one cyaphido ligand.  Synthesis is achieved from the precedent cation [Ru(dppe)2(CΞP)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiCΞP.  The heteroleptic analogue trans‐[Ru(dppe)2(CΞN)(CΞP)] is also prepared from the same cation and NaCN; both cyaphido complexes are structurally characterized, enabling the first direct comparison of cyaphide with cyanide, its isoelectronic and isolobal counterpart.  This demonstrates an enhanced p‐acidity for ‐CΞP over ‐CΞN, while computational studies reveal also a degree of p‐donor character for the cyaphido ligand.