Heteroleptic Co(III) bisdithiocarbamato-dithione complexes: Synthesis, structure and bonding of [Co(Et₂dtc)₂(R₂pipdt)]BF₄ (R = Me, 1; Ph, 2; pipdt = piperazin-2,3-dithione) complexes

The reaction between the binuclear cobalt complex, [Co2(Et2dtc)5]+, and Me2pipdt Ph2pipdt ligands has provided almost quantitatively tris-chelate heteroleptic complexes [Co(Et2dtc)2(R2pipdt)]BF4 (1 2). molecular structure of 2 shows metal in a distorted octahedral geometry. nature bonding these been elucidated with support DFT TD-DFT calculations. Both chelating S,S donors work as weak-field ligands. comparison chemical reactivity for homoleptic dithiocarbamate complex [Co(Et2dtc)3] [Co(Et2dtc)2(Ph2pipdt)]+ derivative that global softness σ is significantly higher than due to reduction nephelauxetic effect induced by dithioxamide ligand. kinetics reagents CH2Cl2 followed spectrophotometrically function temperature pseudo-first order conditions respect R2pipdt Kinetic results further mechanism involving one-end reversible dissociation [Co2(Et2dtc)5]+ dimer forming reactive cobalt(III)dithiocarbamato center susceptible attack nucleophiles. effectiveness versatility above an easy clean method provide heteroleptic-dithiocarbamates variety suitable interest applicative purposes.