Chemistry of In(C₅H₅)₃ and Some Heteroleptic Organoindium(III) Derivatives. Crystal and Molecular Structures of In(C₅H₅)₃, (C₅H₅)₃In·PPh₃, and (Me₃CCH₂)₂In(C₅H₅)

Pure In(C₅H₅)₃ has been prepared in high yields from InCl₃ and Li(C₅H₅) in THF solution with the absence of external heating. Neat In(C₅H₅)₃ readily decomposes at 150 °C to form In(C₅H₅)_(s) and cyclopentadiene as the primary products whereas a benzene suspension decomposes under refluxing conditions. In(C₅H₅)₃ forms an isolable 1:1 adduct with PPh₃ but NMe₃, THF, and Et₂O do not form stable adducts. Ligand redistribution reactions with InR₃ (R = Me and CH₂CMe₃) in THF solution provided R₂In(C₅H₅) and RIn(C₅H₅)₂. These heteroleptic organoindium(III) compounds have been isolated as analytically pure crystalline solids, but in THF solution they form equilibrium mixtures of the adducts of InR₃, R₂In(C₅H₅), RIn(C₅H₅)₂, and In(C₅H₅)₃, as appropriate. Crystals of [In(C₅H₅)₃]_n, (C₅H₅)₃In·PPh₃, and [(Me₃CCH₂)₂In(C₅H₅)]_n were characterized by single-crystal X-ray structural studies.