Synthesis, Crystal Structures, and Thermolysis Studies of Heteronuclear Transition Metal Aluminum Alcoholates

Heteronuclear alcoholate complexes [M{Al(O i Pr) 4 } 2 (bipy)] ( 2‐M , M = Fe, Co, Ni, Cu, Zn) and [M{Al(O c Hex) 4 } 2 (bipy)] ( 3‐M , M = Fe, Co, Ni, Zn) are formed by adduct formation of [M{Al(O i Pr) 4 } 2 ] ( 1 ‐ M , M = Fe, Co, Ni, Cu, Zn) with 2,2'‐bipyridine and transesterification reaction with c HexOAc. According to crystal structure analyses, in 2‐M and 3‐M the central transition metal ion M 2+ is coordinated by two chelating Al(OR) 4 – moieties and one bipyridine ligand in an octahedral arrangement. Treating 1‐Cu with 2,2'‐bipyridine leads to a reduction process, whereat the intermediate [Cu{Al(O i Pr) 4 }(bipy) 2 ][Al(O i Pr) 4 ] ( 4 ) could be structurally characterized. During conversion of the iso ‐propanolate ligands in 1‐Cu to cyclohexanolate ligands, Cu 2+ is reduced to Cu + forming [Cu{Al(O c Hex) 4 }(py) 2 ] ( 5 ). UV/Vis‐spectra and results of thermolysis studies by TG/DTA‐MS are reported.