Insertion of MeO2C–CC–CO2Me (DMAD) into the Pd–C bond of the heterodimetallic complex [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd(dmba-C)] (2) (dppm = Ph2PCH2PPh2, dmba-C = metallated dimethylbenzylamine) and [(OC)3{(MeO)3Si}Fe(μ-dppm)Pd(8-mq-C,N)] (3) (8-mq-C,N = cyclometallated 8-methylquinoline) yielded the σ-alkenyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{C(CO2Me)C(CO2Me)(o-C6H4CH2NMe2)}] (7) and [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{C(CO2Me)C(CO2Me)(CH2C9H6N)}] (8), respectively. The latter afforded the adduct [(OC)3{(MeO)3Si}Fe(μ-dppm)Pd{C(CO2Me)C(CO2Me)(CH2C9H6N)}(CNBut)] (9) upon reaction with 1 equiv. of ButNC. The heterodinuclear σ-butadienyl complexes [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{C(Ph)C(Ph)C(CO2Me)(CO2Me)(o-C6H4CH2NMe2)}] (11) and [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{C(Ph)C(CO2Et)C(Ph)C(CO2Et)(CH2C9H6N)}] (13) have been obtained by reaction of the metallate K[Fe{Si(OMe)3}(CO)3(dppm-P)] (dppm = Ph2PCH2PPh2) with [PdCl{C(Ph)C(Ph)C(CO2Me)C(CO2Me)(o-C6H4CH2NMe2)}] or [PdCl{C(Ph)C(CO2Et)C(Ph)(CO2Et)}(CH2C9H6N)], respectively. Monoinsertion of various organic isocyanides RNC into the Pd–C bond of 2 and 3 afforded the corresponding heterometallic iminoacyl complexes. In the case of complexes [(OC)3{(MeO)3Si}Fe(μ-dppm)Pd{C(NR)(CH2C9H6N)}] (15a R = Ph, 15b R = xylyl), a static six-membered C,N chelate is formed at the Pd centre, in contrast to the situation in [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{C(NR)(o-C6H4CH2NMe2)}] (14a R = o-anisyl, 14b R = 2,6-xylyl) where formation of a µ-η2-Si–O bridge is preferred over NMe2 coordination. The outcome of the reaction of the dimetallic alkyl complex [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)PdMe] with RNC depends both on the stoichiometry and the electronic donor properties of the isocyanide employed for the migratory insertion process. In the case of o-anisylisocyanide, the iminoacyl complex [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{C(N-o-anisyl)Me}] (16) results from the reaction in a 1 : 1 ratio. Addition of three equiv. of o-anisylisocyanide affords the tris(insertion) product [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{[C(N-o-anisyl)]3Me}] (18). After addition of a fourth equivalent of o-anisylNC, exclusive formation of the isocyanide adduct [(OC)3{(MeO)3Si}Fe(μ-dppm)Pd{[C(N-o-anisyl)]3Me}(CN-o-anisyl)] (19) was spectroscopically evidenced. In the complex [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)Pd{[C(N-o-C6H4COCH2)]2Me}] (20), the σ-bound diazabutadienyl unit is part of a 12-membered organic macrocyle which results from bis(insertion) of 1,2-bis(2-isocyanophenoxy)ethane into the Pd–Me bond of the precursor complex [(OC)3Fe{μ-Si(OMe)2(OMe)}(μ-dppm)PdMe]. In contrast, addition of two equivalents of tert-butylisocyanide to a solution of the latter afforded [(OC)3{(MeO)3Si}Fe(μ-dppm)Pd{C(NBut)Me}(CNBut)] (21) in which both a terminal and an inserted isocyanide ligand are coordinated to the Pd centre. In all cases, there was no evidence for competing CO substitution at the Fe(CO)3 fragment by RNC. The molecular structures of the insertion products 8·CH2Cl2 and 16·CH2Cl2 have been determined by X-ray diffraction.