Triosmium clusters derived from aldehydes, ketones, and ketens and their interconversions

Abstract
Acyl and enolato-complexes of types [Os3(CO)10(µ-OCR)H](R = CH3, C5H11, C6H13, PhCH2, Me2CH, or Ph) or [Os3(CO)10(µ-OCHCR′2)H](R′= H, Me, or Ph) have been obtained by oxidative addition of aldehydes at [Os3(CO)12] or by insertion of keten or substituted ketens into an Os–H bond of [Os3(CO)10H2]. In certain cases the interconversion of enolato- and acyl complexes was established and in other cases inferred from their reactivity. The acyl complexes where R = CH3, Ph, or Ph2CH (derived from isomerisation of the enolato-complex where R = Ph) decarbonylate at the ligand to give products derived from the alkyl complexes formed. Most acyl complexes (R = CH3, C5H11, C6H13, or PhCH2) decarbonylate, however, only at the metal with subsequent hydrogen-atom transfer to and from the ligand to give complexes of type [Os3(CO)93-R″CCHO)H2] containing a co-ordinated formyl group. Analogous species were obtained from cyclohexanone and [Os3(CO)12] or from cyclohexenone and [Os3(CO)10H2]. All the complexes with organic ligands containing oxygen have Os–O bonds.

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