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The reaction between the binuclear cobalt complex, [Co 2 (Et 2 dtc) 5 ] + , and Me 2 pipdt and Ph 2 pipdt ligands has provided almost quantitatively the cobalt tris-chelate heteroleptic complexes [Co(Et 2 dtc) 2 (R 2 pipdt)]BF 4  ( 1  and  2 ). The molecular structure of  2  shows the metal in a distorted octahedral geometry. The nature of the bonding in these complexes has been elucidated with the support of DFT TD-DFT calculations. Both chelating S,S donors work as weak-field ligands. The comparison of the chemical reactivity for the homoleptic dithiocarbamate complex [Co(Et 2 dtc) 3 ] and the heteroleptic [Co(Et 2 dtc) 2 (Ph 2 pipdt)] +  derivative shows that the global softness σ is significantly higher in [Co(Et 2 dtc) 2 (Ph 2 pipdt)] +  than in the homoleptic dithiocarbamate complex, due to a reduction of nephelauxetic effect induced by the dithioxamide ligand. The kinetics for the reaction between the reagents in CH 2 Cl 2  has been followed spectrophotometrically as a function of temperature in pseudo-first order conditions with respect to R 2 pipdt ligands. Kinetic results further support a reaction mechanism involving a one-end reversible dissociation of the [Co 2 (Et 2 dtc) 5 ] +  dimer forming a reactive cobalt(III)dithiocarbamato center susceptible to attack by nucleophiles. The effectiveness and versatility of the above reaction is an easy and clean method to provide heteroleptic-dithiocarbamates with a variety of suitable ligands of interest for applicative purposes.

journal of coordination chemistry

Heteroleptic Co(III) bisdithiocarbamato-dithione complexes: Synthesis, structure and bonding of [Co(Et 2 dtc) 2 (R 2 pipdt)]BF 4  (R = Me, 1; Ph, 2; pipdt = piperazin-2,3-dithione) complexes