Trimerization of acetylferrocene and of (acetylcyclopentadienyl)tricarbonyl-manganese proceeds efficiently in the presence of ethanol and tetrachlorosilane. The resulting 1,3,5-trisubstituted benzenes have been characterized by X-ray crystallography and compared with the structure of (1,3,5-triphenylbenzene)tris(tricarbonylchromium). The efficacy of EtOHSiCl4 as a combined reagent for the trimerization of polycyclic ketones is also discussed. Finally, the synthesis and structure of [CpMn(CO)2]2(µ-C=CHPr), derived from the reaction of cymantrene with butyllithium and phenylacetyl chloride at room temperature, is described.Key words: ketone, condensation, cyclization, organometallics, arenes.
Acetylferrocene readily forms an adduct with BF 3 . The product is a neutral model for protonated acetylferrocene, a species that is a crucial intermediate in the formation of 1,3,5-trisferrocenyl-benzene and other conjugated heterometallic derivatives by cyclocondensation. The title compound's structure was determined in the solid state by X-ray diffraction and its spectroscopic properties were examined in detail, particularly the electronic excitation spectrum, which confirms the previous identification of the in situ generated protonated ketone.Résumé : L'acétylferrocène forme facilement un adduit avec le BF 3 . Le produit est un modèle neutre pour un acétylferro-cène, une espèce qui est un intermédiaire crucial dans la formation du 1,3,5-trisferrocényl-benzène et d'autres dérivés hété-rométalliques par cyclocondensation. La structure du composé mentionné dans le titre a été déterminée à l'état solide par diffraction des rayons X et on a examiné ses propriétés spectroscopiques en détail, en particulier son spectre d'excitation électronique qui confirme l'identification antérieure de la cétone protonée générée in situ.Mots-clés : cétones organométalliques, adduits avec le BF 3 , cations ferrocényles, calculs d'après la théorie de la fonctionnelle de la densité (TFD).[Traduit par la Rédaction]
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