Solid-state, thermally stable tetramethylguanidinium N,N-diethylcarbamate [TMGH][O2CNEt2] was prepared from tetramethylguanidine (TMG), N,N-diethylamine and carbon dioxide (1 atm). The reaction of [TMGH][O2CNEt2] with TiCl4 in toluene afforded [TMGH]2[TiCl6] and TiCl2(O2CNEt2)2. The tetrachlorides of titanium, zirconium and hafnium were effectively converted into the respective mixed dichloridedicarbamates, MCl2(O2CNEt2)2, by the reaction with either silver diethylcarbamate or the corresponding homoleptic metal N,N-diethylcarbamate, M(O2CNEt2)4. The titanium and hafnium derivatives are trinuclear in the solid state according to X-ray diffraction analysis (M = Ti) and DFT calculations (M = Hf). Instead, ZrCl2(O2CNEt2)4 was obtained as a mixture of two isomers presumably holding dinuclear and trinuclear structures, according to DFT calculations. Difluoride-dicarbamate TiF2(O2CNEt2)4 was prepared in a similar way as the homologous Cl-compound. All the products were characterized by analytical and spectroscopic methods, and by X-ray diffraction in the cases of [TMGH]2[TiCl6] and Ti3 Cl6(m-O2CNEt2)6. The complex Hf4Cl4(O)2(O2CNEt2)6[O(CH2)3CHO]2 was isolated in low yield in crystalline form from a thf solution of HfCl2(O2CNEt2)2, and then X-ray characterized.