Treatment of [Pd{CH2C(CH3)CH2}(Ph2PPy)Cl] (Ph2PPy = 2-(diphenylphosphino)pyridine) with cis-[Pd(tBuNC)2Cl2] in dichloromethane affords the mixed isocyanide-tertiary phosphine complex cis-[Pd(tBuNC)(Ph2PPy)Cl2], in which the Ph2PPy is a monodentate P-donor, and [{Pd[CH2C(CH3)CH2]Cl}2]. The steric effects of the Ph2PPy bridging ligand in determining the reaction course is discussed. The complex cis-[Pd(tBuNC)(Ph2PPy)Cl2] Was crystallographically characterized: P2(1)/n, a = 15.143(2), b = 9.527(1), c = 17.517(4) angstrom, beta = 113.96(1)-degrees, V = 2309.4(7) angstrom3, Z = 4. The final R value was 0.044, R(w) = 0.046 for the 3078 reflections with I > 3sigma(I).