A key intermediate for the hydration reaction of [Cr(eta(6)-silabenzene)(CO)(3)], hydrido(eta(5)-silacyclohexadienyl)chromium complex, was successfully synthesized by the reaction of silabenzene complex with 2 mol equiv of H2O. X-ray diffraction Study revealed that the hydroxy group on the central silicon atom is located at the endo position to the metal moiety. The treatment of the endo adduct with excess of D2O resulted in the stereoselective formation of 1-silacyclohexa-2,4-diene bearing a deuterium atom at the methylene position.