Organocobalt cluster complexes. 20. Novel chemistry of acyl- and aroylmethylidynetricobalt nonacarbonyl complexes. Unusual thermal ketone decarbonylation reactions

Surface organometallic chemistry: Facile μ2-carbene to μ3-carbyne transformation of organocobalt carbonyls on silica surface

“…In this work, we have produced clear evidence that the silica surface may induce under very mild conditions, a facile process of cluster aggregation or decarboxylation, which usually requires in solution the presence of strong acidity [9,10] or a thermal treatment [13,14], although it is known that the acidity of surface silanol groups is very weak [15]. In conclusion, our work is an interesting additional observation which confirms the role of the silica surface as an unusual reaction medium in the growing area of organometallic chemistry for synthetic purposes mediated by the surface of an inorganic oxide [3].…”

“…The easy decarboxylation of the ester-type complexes 2a is an additional example of a similar chemical process such as the decarbonylation of [l 3 -RC(O)C]Co 3 (CO) 9 type ketones, observed by SeyferthÕs group [13] as well as the decarboxylation of the ROC(O)Co(CO) 4 type ''esters'', observed by us a decade ago [14]. It is worth noting also that the production of the ester-type complex such as, [l 3 -CH 3 C(O)OC]Co 3 (CO) 9 (2a, R = Me), requires a complex synthesis involving the acylation of the lithium salt (l 3 -LiOC)Co 3 (CO) 9 by acetyl chloride [8a].…”