The synthesis of the azavinylidene and azavinylidene-bridged compounds Ir(=N=CPli2)-(diolefinXPCys) (5, diolefin =tetrafluorobenzobarrelene (TFB); 6, diolefin =1,5-cyclooctadiene (COD)) and [Ir(M-N=CPh2)(diolefin)]2 (7, diolefin = COD; 8, diolefin = TFB) is described. The azavinyhdene derivatives 5 and 6 were prepared by reaction of the corresponding squareplanar methoxy complex Ir(OMe)(diolefin)(PCys) with benzophenone imine, whereas the azavinylidene-bridged 7 and 8 were similarly obtained from [Ir(/z-OMeXdiolefin)]2 (diolefin = COD, TFB). The complexes 7 and 8 react with CO to give [Ir(M-N=CPh2)(CO)2]2 (9), which affords [Ir(M-N=CPh2)(CO)(PCy3)]2 (10) in the presence of PCys. The preparation of the related compounds [Rh(/t-N=CPh2)(diolefin)]2 (diolefin = COD (13), TFB (14)), [Rh(«-N=CPh2)(CO)2]2 (15), Rh2(/t-N=CPh2)2(CO)3PCy3 (16), and [Rh(/t-N=CPh2)(CO)(PCy3)]2 (17) is also reported. The structure of 14 was determined by an X-ray investigation. 14 crystallizes in the space group PI with a =16.468(5) k,b = 16.569(5) A, c =18.139(5) Á, a =66.03(1)°, ß —74.32(2)°, y=89.71(2)°, and Z = 4. The molecular structure reveals that the core of the molecule is formed by a Rh2N2 skeleton in a bent configuration. We thank the DGICYT (Project PB92-0092, Programa de Promoción General del Conocimiento) and the EU (Project: Selective Processes and Catalysis involving Small Molecules). M.O. and E.O. thank the Diputación General de Aragón (DGA) for grants. Peer reviewed