Classical methods for the synthesis of indan-1,3-dione derivatives failed when applied to their tricarbonylchromium complexes. The desired 2-substituted (η6-indan-1,3-dione)tricarbonylchromium complexes were prepared starting from protected indan-1,3-dione derivatives such as bis(dioxolanes) and enol ethers. Tricarbonylchromium complexes of indan-1,3-dione having at least one hydrogen at C-2 are unstable. Nevertheless, ethylation of 2-methyl(η6-indan-1,3-dione)tricarbonylchromium and methylation of 2-ethyl(η6-indan-1,3-dione)tricarbonylchromium were possible and proceeded with high stereoselectivity.