Clathrate and inclusion compounds: Part V. An infrared and Raman study of the decomposition of the Hofmann aniline clathrates M(NH3)2Ni(CN)4.2C6H5NH2 {M = Cd(II) and Ni(II)}

The time-dependent changes which are observed in the infrared and Raman spectra of samples of the two Hofmann aniline clathrates M(NH₃)₂Ni(CN)₄.an₂ {M = Cd(II), Ni(II), an = C₆H₅NH₂} indicate the occurrence of a solid state ligand replacement reaction in which the aniline guest molecule replaces the coordinated ammonia to give Man₂Ni(CN)₄ as the final product. The rate of replacement is greater for the cadmium than for the nickel clathrate, and for both clathrates evacuation of the sample greatly increases the rate of replacement. The Man₂Ni(CN)₄ complexes can themselves act as host lattices forming clathrates containing guest molecules such as aniline.