Spectroscopic studies on adsorbed metal carbonyls. Part 3. Interaction of [Os3(CO)12] with silica, alumina, and titania

Publisher Website
Google Scholar
Abstract
The interaction of [Os3(CO)12] on silica, alumina, and titania gives, as the initially observed adsorbate, [Os3H(CO)10(µ-O–oxide)](2)(on silica) or [Os3(CO)10(µ-O–oxide)(OH)](3). Following analyses of the model compounds [Os3XY(CO)10](X = Y = H; X = H, Y = OMe; X = Y = OEt), the structure of this species on alumina was investigated by Os L(III) edge extended X-ray absorption fine structure. Both (2) and (3) can be fitted to the data, but the latter affords more reasonable Debye–Waller factors. Subsequent pyrolysis generates a mixture of [Os(CO)3]n and [Os(CO)2]n species. This process is reversible on silica. Attempts to simulate the v(CO) absorptions of a 13CO-enriched version of the pyrolysis products to simple mono- and di- nuclear models were unsuccessful. This evidence, together with the electronic absorption spectra of these materials, suggests a trimeric array as the smallest likely unit, probably with some metal–metal bonding. A by-product from the reaction with alumina and titania was [Os3H(Cl)(CO)10]. Interaction of [Os3(CO)12] with a hydroxylated cleaved mica crystal in refluxing n-octane gave rise to the pyrolysis products [Os(CO)3]n and [Os(CO)2]n.

This publication has 0 references indexed in Scilit: