A Monometallic Bis(cyaphido) Complex

The first example of a bis(cyaphido) complex, trans‐[Ru(dppe)2(C≡P)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(C≡P)]+ via sequential coordination and desilylation of the phosphaalkyne Me3SiC≡P. The heteroleptic analogue trans‐[Ru(dppe)2(C≡N)(C≡P)] 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 π‐acidity for −C≡P over −C≡N, while computational studies reveal also a higher π‐donor character for the cyaphido ligand. A bis(cyaphido) complex is achieved for the first time, demonstrating the viability of incorporating multiple cyaphido ligands at one metal center. Comparison with the heteroleptic C≡N/C≡P analogue offers the first direct experimental comparison of cyaphide with cyanide. A degree of cooperative delocalization within the bis(cyaphido) complex illustrates the cyaphido ligand exhibiting some π‐donor, in addition to its π‐acceptor, character.