The new complexes (aa-H2)[CrF4(aa)]Cl, where aa = ethylenediamine, 1,2-diaminopropane or 1,2-diaminocyclohexane, have been systematically synthesized and characterized. The crystal structure of (en-H2)[CrF4(en)]Cl (en = ethylenediamine) has been resolved indicating that the four fluorine atoms are ligands and the chloride is ionic. The cation is the diprotonated ethylenediamine ligand. Synthesis of the analogous complex with 1,3-diaminopropane (tn) failed. The hydrolysis of these complexes with concentrated HBr give compounds of formula [CrF2(H2O)2(aa)]Br, which upon solid phase heating yield the dehydrated [CrF2Br(H2O)(aa)]. © 1984 Verlag Chemie GmbH.