The complexes [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppm)PdR] (R = alkyl, aryl) have been obtained either by treatment of [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppm)PdCl] 1a with organolithium or Grignard reagents or, in the case where R = Me, by reaction of [PdCl(Me)(COD)] (COD = 1,5-cyclooctadiene) with the metallate K[Fe{Si(OMe)₃}(CO)₃(dppm-P)] 2a. When dppa was used as an assembling ligand, reaction of the hydrido complex mer-[HFe- {Si(OMe)₃}(CO)₃(dppa-P)] 7b with [PdCl(Me)(COD)] or [Pd(η³-allyl)(µ-Cl)]₂ proceeded via elimination of methane or propene, respectively, to afford [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppa)PdCl] 1b and not via HCl elimination which would have resulted in hydrocarbyl complexes. However, reaction of 7b with [PdX(R)(TMEDA)] (X = Cl, R = Me; X = I, R = Ph; TMEDA = Me₂NCH₂CH₂NMe₂) afforded the hydrocarbyl complexes [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppa)PdMe] 3b or [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppa)PdPh] 5b. The latter and [(OC)₃{(MeO)₃Si}Fe(µ-dppa)Pd(η³-allyl)] 8b were obtained by reaction of the carbonylmetallate 2b with [PdCl(Me)(COD)], [PdI(Ph)(TMEDA)] or [Pd(η³-allyl)(µ-Cl)]₂, respectively. The stabilizing but labile four-membered µ-η²-SiO→Pd bridging interaction facilitates CO insertion into the Pd–Me bond of 3a or 3b to afford the corresponding acetyl complexes. For comparison, [(OC)₃{(MeO)₃Si}Fe(µ-dppm)Pd(8-mq)] 6a which contains a stable five-membered (C,N) chelate at Pd did not insert CO under similar conditions. The reaction of CO with the benzyl derivative [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppm)Pd(CH₂Ph)] 4a was more complex since the resulting acyl [(OC)₃Fe{µ-Si(OMe)₂(OMe)}(µ-dppm)Pd{C(O)CH₂Ph}] 11a rearranged into the µ-siloxycarbene complex [(OC)₃Fe{µ-C(CH₂Ph)OSi(OMe)₃}(µ-dppm)Pd(CO)] 12a. Comparisons are made between complexes containing dppm or dppa and different R groups. The structures of complexes 1b, 5b·THF and 6a·hexane have been determined by X-ray diffraction.