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 degreesC 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)(3)In.PPh3, and [(Me3CCH2)(2)In(C5H5)](n) were characterized by single-crystal X-ray structural studies.