The microdetection of particulates from organometallic compounds: I. Metal acetylacetonate chelates

Abstract

The new technique of organic particulate analysis (OPA) has been employed to evaluate the thermal decomposition of metal acetylacetonate chelates. Of the 23 compounds thus evaluated, 13 were found to give organoparticulation signals at temperatures <190 °C as indicated by their effect on the output current of an ion chamber detector. In some instances, very strong particulation was observed, particularly with the transition metal acetylacetonates, such as Co(II), Co(III), Fe(III), Cr(III), and Mn(III). In an attempt to characterize the nature of the particulates derived from these compounds, mass-spectral data were obtained on the effluent species arising from the thermal decompositions of the strongest particulate emitting metal acetylacetonates. The results showed that acetylacetone was the major component identified in both particulate and vapor effluents. With the exception of Cr(III) acetylacetonate, no metal was detected in these effluents. The OPA technique enabled the relative thermal stabilities of the metal acetylacetonates to be ascertained. Zn acetylacetonate was found to have the lowest thermal stability and the alkaline earth compounds the highest; the transition metal acetylacetonates exhibit intermediate thermal stabilities. Since a certain critical minimum particulate size (i.e., 25 Å) seems to be necessary to produce a response on the ion chamber detector instrument, vapor-phase association of acetylacetone molecules may be occurring. This association would most probably occur through H-bonded species involving the enol form of the 1,3-diketone.