Photolytic decarbonylation of (eta(6)-arene)Cr(CO)(3) in the presence of HSiCl3 initially yields (eta(6)-arene)Cr(CO)(2)H(SiCl3) followed by (eta(6)-arene)Cr(CO)(2)(SiCl3)(2). An additional species, a novel chromium dihydride, (eta(6)-arene)Cr(CO)(H)(2)(SiCl3)(2), which is generated en route to the formation of (eta(6)-arene)Cr(CO)(2)(SiCl3)(2) has been isolated and characterized. The two hydride ligands of this complex show fluxional behavior. X-ray structural elucidations of (eta(6)-arene)Cr(CO)(H)(2)(SiCl3)(2), where eta(6)-arene = fluorobenzene or mesitylene, are presented. The data more strongly support a formulation as Cr(IV) dihydride derivatives as opposed to sigma-bonded side-on H-SiCl3 groups. In addition, the data do not support formulation as eta(2)-dihydrogen complexes.