The synthesis, characterization, and exploratory chemistry of two classes of alkene-platinum-silyl complexes, which have been postulated as hydrosilation intermediates, are described in this report. The unique dimeric complexes 1, [R3Si(mu-Cl)(eta(2)-COD)Pt](2) {R3Si = Et3Si, MeCl2Si, Me2ClSi, "(EtO)(3)Si", PhMe2Si, and (Me3SiO)Me2Si; COD = cycloocta-1,5-diene}, and the bis-silyl complexes 2, (eta(4)-COD)Pt-(SiR3)(2) (R3Si = Cl3Si, MeCl2Si, Me2ClSi, and PhMe2Si), are formed from the sequential reaction of 2 and 4 equiv of the corresponding hydrosilanes, respectively, with Pt(COD)Cl-2 in the presence of a small excess of COD. Complexes 1 are stable for many days in solution at room temperature but decompose via slow elimination of chlorosilane. Some of the bis-silyl compounds 2 are stable for extended periods under inert atmosphere and especially below 0 degreesC, either in the solid state or in solution (in the presence of a small excess of free COD). Complexes 2 display catalytic activity as discrete, molecular, and mononuclear species for hydrosilation and isomerization reactions. Compound 2c (R3Si = MeCl2Si) was fully characterized via multinuclear NMR spectroscopy and X-ray crystal structure analysis. The facile H-transfer rather than Si-transfer to bound COD provides experimental support for the sequence of insertive steps in the Chalk-Harrod catalytic cycle, at least for Pt-catalyzed hydrosilation.