Toluene solvates of MCl4·nIDipp (n = 1, M = Ge, Sn; n = 2, M = Sn) complexes have been synthesized and structurally characterized. Mass spectrometric studies indicate that upon heating complexes of a 1:1 composition MCl4·IDipp undergo sublimation and dissociation into the components, while a complex of 1:2 composition SnCl4·2IDipp does not exist in the gas phase. Thermal decomposition of MCl4·IDipp is accompanied by H/Cl exchange by formation of C27H34Cl2N2 molecules. In contrast, upon decomposition or prolonged storage of SnCl4·2IDipp a chlorination of IDipp takes place by formation of C27H36Cl2N2. Experimental findings are in qualitative agreement with the results of DFT computations.