The reaction of CpM(CO)(2)(mu-PPh2)Mo(CO)(5) (M = Mo, W) with phosphine imide was regiospecific with the isocaynide ligand regiospecifically coordinated to the Mo atom to produce bimetallic isocyanide complexes CpM(CO)(2)(mu-PPh2)Mo(CO)(4)(CNR) (M = Mo, W; R = Pr, CH2Ph, Pr-i). A single-crystal study of cis-CpW(CO)(2)(mu-PPh2)Mo(CO)(4)(CNPr) was performed.