A Cyanamido-Bridged Diiridium Complex: A Reactive Building Block for Polynuclear Cyanamido Complexes

[Cp*IrCl2]2 reacts with 2 equiv of Na2NCN to afford the NCN-bridged diiridium complex [Cp*Ir(μ2-NCN-N,N)]2 (5), which undergoes further reactions with donor molecules such as CO and phosphines. Complex 5 works as an excellent building block for the synthesis of the NCN-capped heterotrinuclear complexes [(Cp*Ir)2(ML)(μ3-NCN-N,N,N)2]+ (ML = Rh(cod), CpRu, Pd(η3-C3H5)) on reactions with cationic group 8−10 metal complexes such as [Rh(cod)(acetone)n]+, [CpRu(MeCN)3]+, and [Pd(η3-C3H5)(acetone)n]+, while the dimerization of 5 leads to the cubane-type tetrairidium complex [Cp*Ir(μ3-NCN-N,N,N)]4.