Kinetics of adduct formation between Heteropolymetallic targets (µ4-O) N4 Cu4-х Mx X6 and Cu (NS)2 reagent in Nitrobenzene

Abstract

The rate laws for the earliest events in the specific stoichiometric monotrahsmetalation of heteropolymetallic targets (b-O)(amine)4Cu4-xMxX6w, here the amine ligand is pyridine (py) or monodentate N,N, diethylnicotinamide (N), x is 1-3, M is Co or Ni(H20), X is C1 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 methylisopropylidinehydrazine- carbodithioate,d epends on the amine, M, M', x and X. The observed event can be the formation of reaction precursors PI, P2 or P3, metal exchange within the precursors, rearrangement of successors St, SZ or S3 complexes or their dissociation to separate products. The kinetic and thermodynamic data are compared with those of a neutral monomeric target Cu(ac.a~.c)o~n taining only oxygen donor atoms. The structural-mechanistic origins of monotransmetalation specificity and adduct formation in these systems are discussed.