1,10-Phenanthroline-5,6-dione Complexes of Middle Transition Elements: Mono- and Dinuclear Derivatives

The synthesis and the characterization of several mono- and dinuclear middle transition metal derivatives of 1,10-phenanthroline- 5,6-dione, 1, are presented. The reaction of 1 with CrCl2(THF)2 gives CrCl2(O,O0-C12H6N2O2)(THF)2, 2, while the halides of iron(II), cobalt(II) and nickel(II) afford adducts of general formula MX2(N,N0-C12H6N2O2), M = Fe, 4, Co, 5, X = Cl; M = Ni, 6, X = Br. DFT calculations on CrCl2(L)(THF)2 with L = O,O0-C12H6N2O2 or O,O0-C14H8O2 allowed a direct comparison of the coordination properties of 9,10-phenanthrenequinone and 1,10-phenanthroline-5,6-dione to be made. Dinuclear compounds of general formula CrCl2(THF)2(O,O0-C12H6N2O2-N,N0)MXnLm, M = Zr, 7, X = Cl, n = 4, m = 0; M = Cr, 8, X = Cl, n = 2, L = THF, m = 2; M = Fe, 9, Co, 10, X = Cl, n = 2, m = 0; M=Ni, 11, X = Br, n = 2, m = 0, are prepared from 2 and the corresponding metal halide, while VCp2(O,O0-C12H6N2O2-N,N0)FeCl2, 12, is synthesized by reacting 4 with VCp2. The electronic properties of the different complexes are investigated by magnetic moment measurements and EPR spectroscopy.