Thermal latent coordination compounds

Abstract

Complexes of the type M(Pa) 2 (HAz) 2 and M(QA) 2 (HAz) 2 (M=cobalt(II) and nickel(II); HPa=picolinic acid, HQa=quinaldic acid; HAz=azoles like imidazole (HIm), pyrazole (HPz), benzimidazole (HBzIm) etc.) show a similar thermal behaviour. In the first step of decomposition the corresponding azolinium picolinates or quinaldinates (H 2 AzPa, H 2 AzQa) are split off with formation of polymeric mixed ligand complexes M(Pa)(Az) or M(Qa)(Az). X-ray analysis of Co(Qa) 2 (HBzIm ) 2 XIIIa illustrates a proton transfer and a subsequent thermal removal of benzimidazolinium quinaldinate (H 2 BzImQa) : Hydrogen bridges from pyrrole nitrogen of the benzimidazole to the non-coordinated oxygen of the quinaldinate predetermine the thermal initiated proton transfer. The high volatility of the heterocyclic acids and the nitrogen coordination are responsible for the formation of the mixed ligand complex Co(Qa)(BzIm) XIVa. Exceptions are the complexes M(Pa) 2 (HPz) 2 XIa-b and M(Qa) 2 (HIm) 2 XVIIa-b. Pyrazole is eliminated from the complexes XIa-b with formation of the solvent-free inner complex M(Pa) 2 XIIa-b. From compounds XVIIIa-b quinaldic acid or their decomposition products are split off and a high temperature modification of M(Im) 2 XVIIIa-b is formed at elevated temperature. XVIIIa-b are decomposed to the cyanides M(CN) 2 similarly to the thermal behaviour of Cu(Im). In the first step the thermal degradation of imidazole and pyrazole adducts of copper(II) picolinates and quinaldinates is characterized by the elimination ofazoles. The reason for this thermal behaviour-is the weaker coordination ofthe azole heterocycles in copper chelate compounds.