The complex [Pd(azoMe)(κ 1 -dppm)(κ 2 -dppm)]TfO (azoMe ) 2-(4′-tolylazo)-5-methylphenyl, dppm ) bis(diphenylphosphino)methane, TfO ) CF 3 SO 3 ) reacts at room temperature with aryl azides N 3 Ar to give, in moderate to high yields, iminophosphorane complexes [Pd(κ 2 -azoMe-C,N′){κ 2 -PPh 2 CH 2 P(dNAr , NO 2 -3 (3c), MeO-4 (4a), Me-4 (4b), NO 2 -4 (4c)]. In all cases, there is a linear correlation between δ(P) (ppm) of both phosphorus atoms and temperatureIn the ortho-substituted complexes 2a-c and the nitro derivatives 3c and 4c, crossing of the two δ/T plots of each complex is not observed and the change in chemical shift with temperature is small or nil, |a 1 |, |a 2 | ) (0-12) × 10 -3 ppm/°C. In the other complexes, the gradient of one of the straight lines is positive (a 1 ≈ 26 × 10 -3 ppm/°C) and that of the other is negative (a 2 ≈ -7.5 × 10 -3 ppm/°C). Both lines cross in the range 0-25 °C. 4b reacts with [Au(acac)PPh 3 ] (1:2) to give [Pd(azoMe-C,N′){PPh 2 C(AuPPh 3 ) 2 P(dNAr)Ph 2 -P,N}] [Ar ) ]. [Pd(azoMe-C,N′)(κ 2 -dppm)]TfO reacts with NaN 3 to give [Pd 2 (azoMe) 2 (µ 2 -N 3 )(µ 2 -dppm) 2 ]TfO (6). The crystal structure of 4b is reported.