Revealing the Role of the Cyaphide Ion as a Bridging Ligand in Heterometallic Complexes

The synthesis of heterometallic transition metal complexes featuring bridging cyaphide ions (C≡P(−)) is reported. These are synthesized from reactions of Au(IDipp)(CP) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) with electron‐rich, nucleophilic transition metal reagents, affording Au(IDipp)(μ(2)−C≡P)Ni((Me)I( i )Pr)(2) ((Me)I( i )Pr=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) and Au(IDipp)(μ(2)−C≡P)Rh(Cp*)(PMe(3)). These studies reveal that, in contrast to the cyanide ion, bimetallic cyaphido complexes strongly favor a η(1) : η(2) coordination mode that maximizes the interaction of the second metal (Ni, Rh) with the π‐manifold of the ion (and not the phosphorus atom lone pair). End‐on bridging can be effectively unlocked by blocking the π‐manifold, as demonstrated by reaction of Au(IDipp)(μ(2)−C≡P)Rh(Cp*)(PMe(3)) with an electrophilic transition metal reagent, W(CO)(5)(THF), which affords the heterotrimetallic compound Au(IDipp)(μ(3)−C≡P)[Rh(Cp*)(PMe(3))][W(CO)(5)].