Thermal decomposition of dinuclear complexes LM(μ-OOCR)4ML (L is α-substituted pyridine)

Influence of the nature of organic ligands on the character of thermal decomposition products of CoII and NiII pivalate complexes with amino derivatives of pyridine

“…The thermolysis of mononu clear cobalt complexes 4, 6, 8, and 12 differs from that observed previously for other cobalt pivalates. Thus, co balt oxide or a mixture of oxide and cobalt metal rather than volatile octanuclear cluster 14 (see Refs 21,21,23,and 24) are obtained as the final decomposition products of monomers 4, 6, 8, and 12 (see Table 2). Unlike other known di and polynuclear nickel(II) pivalates, which give nickel oxide as the final decomposition product, 20,21,23,24 the thermolysis of all mononuclear nickel complexes in vestigated in the present study afforded only nickel metal (see Table 2).…”

“…The phase composition of the final product substantially depends on the nature of both the metal and the substituent in the α position of the api cal organic ligand, which is an intramolecular reducing agent and stimulates intramolecular redox reactions dur ing the decomposition. 20- 22 Thus, the thermolysis of di nuclear manganese and iron pivalates (M = Mn or Fe) does not afford metals in spite of the presence of strong reducing agents such as aminopyridine ligands L. 20, 21 The presence of active CH 3 and NH 2 groups in the apical pyri dine molecules in copper derivatives leads to deeper in tramolecular redox processes and the formation of copper metal as the solid decomposition product. 20- 22 The ther molysis of tetracarboxylate complexes with nickel atoms affords a metallic phase only in the presence of apical 2,3 di methylpyridine molecules.…”