The silyl palladium complexes (dcpe)PdH(SiHtBu2) and (dcpe)Pd(SiHMe2)2 display NMR spectra that vary with temperature. The dynamic NMR behavior is consistent with long-lived σ-complexes as intermediates. In the case of (dcpe)PdH(SiHtBu2), the intermediate is believed to be a symmetric complex with doubly bridged hydrogen atoms between the silicon and palladium. Dynamic interchange of the two silicon atoms in (dcpe)Pd(SiHMe2)2 is consistent with an intermediate Si−Si σ-complex.