The kinetics of adduct formation between heteropolymetallic targets (μ 4-O)N 4Cu 4− xM xX 6 and Cu(NS) 2 reagent in nitrobenzene

Abstract

The rate laws for the earliest events in the specific stoichiometric monotransmetalation of heteropolymetallic targets (μ 4-O)(amine) 4Cu 4− x M x X 6, where the amine ligand is pyridine (py) or monodentate N, N,-diethylnicotinamide (N), x is 1–3, M is Co or Ni(H 2O), X is Cl or Br, by transmetalators M′(NS) 2 and their solution adduct formation by reagent Cu(NS) 2 in nitrobenzene, where M′ is Co, Ni or Zn and NS is monoanionic S-methylisopropylidinehydrazine-carbodithioate, depends on the amine, M, M′, x and X. The observed event can be the formation of reaction precursors P 1, P 2 or P 3, metal exchange within the precursors, rearrangement of successors S 1, S 2 or S 3 complexes or their dissociation to separate products. The kinetic and thermodynamic data are compared with those of a neutral monomeric target Cu(ac.ac.) 2 containing only oxygen donor atoms. The structural-mechanistic origins of monotransmetalation specificity and adduct formation in these systems are discussed.