Influence of the nature of organic components in dinuclear copper(II) pivalates on the composition of thermal decomposition products

Tetrabridged dinuclear complexes ((2-NH₂)C₅H₄N)₂Cu₂(μ₂-OOCCMe₃)₄ (2·С₆Н₆) and ((3-NH₂)C₅H₄N)₂Cu₂(μ₂-OOCCMe₃)₄ (3) and the cocrystallization product ((4-NMe₂)C₅H₄N)₂Cu(η²–OOCCMe₃)₂·2((4-NMe₂)C₅H₄N)₂Cu₂(μ₂-OOCCMe₃)₄ (4) were synthesized by the reaction of the polymer [Cu(OOCCMe₃)₂]_n (1) with aminopyridine ligands (L) of different nature (Cu: L = 1:1) in С₆Н₆. The solid-state thermal decomposition of these compounds was studied by differential scanning calorimetry and thermogravimetry, and their electrochemical behavior was investigated by cyclic voltammetry. All newly synthesized complexes were studied by X-ray diffraction, the magnetic properties of the complexes were investigated, and ESR measurements were performed.     

Pivalates with the M<Superscript>II</Superscript><Subscript>4</Subscript>O<Subscript>4</Subscript> cubane core (M = Co,Ni): synthesis,structure, magnetic properties,and solid-state thermolysis

Methods were developed for the controlled thermal synthesis of high-spin cubane-like pivalates {M^II ₄(μ₃−OR)₄} (M = Co or Ni; R = H or Me) starting from mono-and polynuclear complexes. The solid-state thermal decomposition of the known pivalate clusters [M^II ₄(μ₃−OMe)₄−(μ₂−OOCBu^t)₂(η²−OOCBu^t)₂(MeOH)₄] and the new clusters [M₄^II(μ₃)−OH₄(η¹−OOCBu^t)₃−(μ−(NH₂)₂C₆H₂Me₂)₃(η¹−(NH₂)₂C₆H₂Me₂)₃]⁺(OOCBu^t)− (M = Co or Ni) was studied by differential scanning calorimetry and thermogravimetry. The thermolysis of cubane-like CoII and NiII pivalates is a destructive process. The phase composition of the decomposition products is determined by the nature of coordinated ligands and the structural features of the metal core.