Metal complexes of 1,10-Phenanthroline derivatives. VII. Complexes of 1,10-Phenanthroline-2-carbaldehyde hydrazones

A series of substituted hydrazones derived from 1,l0-phenanthroline-2-carbaldehyde and their bis-ligand complexes with bivalent iron and nickel are described. The hydrazones show a gradation in field strength and this is reflected in the spin-state of the iron complexes. The methylhydrazone complex is essentially low-spin over the temperature range 83-363 K but the presence of some spin-free species at high temperatures is evident. Within the same range the dimethylhydrazone complex is essentially high-spin but undergoes significant spin-pairing and the phenylhydrazone complex displays a complete 5T2 → 1A1 spin transition. This transition is very sharp, resulting in a pronounced change in the magnetism, and colour, of the complex within a few degrees. Complexes of the 2-pyridylhydrazone, the methylphenylhydrazone and the diphenylhydrazone are high-spin over the entire experimental temperature range.