The first rhodium complexes of diphosphinoazines [{MCl(1,2-eta: 5,6-eta-CH= CH=CH2CH2CH=CHCH2CH2)}(2) {mu-R2PCH2C(Bu-t)=NN=C(Bu-t)CH2PR2] (R=Ph, Cy, Pr-i,M=Rh,Ir) for the first time.