The decomposition process of ammine lanthanide metallocenes was studied by X-ray diffractometry, spectroscopy and theoretical investigations. A series of ammine-tris(eta(5)-cyclopentadienyl)lanthanide(III) complexes 1-Ln (Lanthanide (Ln)=Sm, Gd, Dy, Ho, Er, Yb) was synthesised by the reaction of [Cp(3)Ln] complexes (Cp=cyclopentadienyl) with liquid ammonia at -78 degrees C and structurally characterised by X-ray diffraction methods, mass spectrometry and vibrational (IR, Raman) spectroscopy. Furthermore, amido-bis(eta(5)-cyclopentadienyl)lanthanide(III) complexes 2-Ln (Ln=Dy, Ho, Er, Yb) were synthesised by heating the respective ammine adduct 1-Ln in an inert gas atmosphere at temperatures of between 240 and 290 degrees C. X-ray diffraction studies, mass spectrometry and vibrational (IR, Raman) spectroscopy were carried out for several 2-Ln species and proved the formation of dimeric mu(2)-bridged compounds. Species 1-Ln are highly reactive coordination compounds and showed different behaviour regarding the decomposition to 2-Ln. The reaction of 1-Ln and 2-Ln with inorganic bases yielded lanthanide nitride LnN powders with an estimated crystallite size of between 40 and 90 nm at unprecedented low temperatures of 240 to 300 degrees C. Temperature-dependent X-ray powder diffraction and transmission electron microscopy (TEM) investigations were performed and showed that the decomposition reaction yielded nanocrystalline material. Structural optimisations were carried out for 1-Ln and 2-Ln by employing density functional (DFT) calculations. A good agreement was found between the observed and calculated structural parameters. Also, Gibbs free energies were calculated for 1-Ln, 2-Ln and the pyrolysis reaction to the nitride material, and were found to fit well with the expected ranges.