Metal chelates of heterocyclic nitrogen-containing ketones, Part XXII. Spectroscopic studies on rhodium(III) complexes of phenyl-2-picolylketone-2-pyridyl hydrazone

Abstract

Mono, bis and tris complexes of rhodium(III) with phenyl-2-picolylketone-2-pyridyl hydrazone (PPKPyH) have been characterized. In every case, the imino-proton of PPKPyH shows marked acidity associated with the coordination to rhodium(III). Electronic spectra show that all complexes are octahedral. The B′-values suggest a strong covalency in the metal-ligand σ-bond and the Dq-values indicate a medium-strong ligand field. The magnetic susceptibility indicates that PPKPyH forms low-spin complexes with rhodium(III).1H n.m.r. spectra show that the tris(ligand) complexes arecis isomers. I.r. spectra show that the ligand is neutral or monobasic tridentate or bidentate. Far i.r. studies show that [Rh(PPKPyH)X3] · 2 H2O (X = Cl, Br or I) aremer isomers. The effect of pH variation on the rection products is also discussed.