Extensively studied cobalt/dimethylglyoxime systems continue to attract considerable research interest as compounds which offer to chemists’ wide range of synthetic, analytical and structural opportunities. In general, two main arrangements of dimethylglyoxime units, trans and cis, have been found for octahedrally coordinated metal atom. Among numerous structurally characterized cobaloxime-type complexes those with trans- positioning of the dimethylglyoxime units prevail while there are only few reports on the cis-arrangement of this ligan. Whereas dimethylglyoxime complexes are generally mononuclear, some specific synthetic conditions (pH, bridging ligands, templating or capping agents) can lead to bi- and trinuclear compounds. The first structurally characterized cis-species: cis-binuclear μ-hydroxy bridged–cobaloxime(III) prepared from transhydroaquacobaloxime(III) treated with conc. aqueous KOH. In turn, Golding and coworkers shown that cisproduct can also be obtained from a series of alkylcobaloximes in chloroform solution when CF3COOH (TFA) is added for a sequential protonation of the DH-residues and removal of axial pyridine and alkyl ligands. According to Tyrlik and coworkers mononuclear tris-cobaloxime (III) can be prepared in acetone solution by one pot reaction of Co(ClO4)2 with an excess of DH2, owing to weak chelating properties of perchlorate anion. In course of our earlier investigations, anions of this type were used in synthesis of cobaloximes and a series of new “classical” mononuclear-trans, nontrivial binuclear Co(III)-trans with μ-peroxo bridge and tris-trinuclear mixed-valence Co(II)(Co(III))2 compounds were obtained. Two types: trinuclear tris Co(II) and mononuclear trans cobaloxime compounds have been obtained by using trifluoromethanesulfonate of Co(II) as starting material in the synthesis of dimethylglyoximate complexes. Anions containing fluorine atoms [AlF6]3-, [SiF6]2-, [BF4]-, [CF3SO3]-, [BeF4]2-, [ZrF6]2- are of special interest in the studies on the Co/DH2 system as it has been revealed recently that many fluorine-atom containing cobaloximes stimulate enzymatic activity in biosynthesis.