Polynuclear Iron‐Oxo/Hydroxy Complexes of Ketoacidoximate Ligands: Synthesis, Structures and Conversion to Ferric Oxide

The polynuclear iron‐oxo/hydroxy complexes containing ketoacidoximate ligands described in this report are [Fe 3 (μ 3 ‐O){O 2 C‐C(C 6 H 5 )=NOCH 3 } 6 (py) 3 ] ( 1 ) (py=pyridine), [Fe 2 (μ 3 ‐O){O 2 C‐C(CH 2 ‐C 6 H 5 )=NO} 2 (H 2 O)(CH 3 OH)] 2 ( 2 ) and [{Fe(μ 2 ‐OH)(O 2 C‐C(CH 3 )=NO)}(dmso)] 6 ( 3 ) (dmso=dimethyl sulfoxide). 1–3 are isolated from the reaction of Fe(NO 3 ) 3 ⋅9H 2 O and in situ generated anions of ketoacidoximate ligand [(HO 2 C‐C(R 1 )=NOR 2 ), where R 1 =CH 3 , C 6 H 5 and CH 2 ‐C 6 H 5 ; R 2 =H or CH 3 ] in H 2 O, followed by crystallization in donor solvents. 1–3 undergo thermal decomposition above 200 °C and form crystalline α ‐Fe 2 O 3 at 600 °C.