Carbon monoxide activation by f-element organometallics. An unusually distorted, carbenelike dihaptoacyl and CO tetramerization

Abstract

Der Chloroneopentyl‐Th‐Komplex (I) absorbiert ein Äquivalent CO unter Bildung des Oxycarben‐Komplexes (II).

Bis(cyclopentadienyl) actinide(IV) compounds. I. The structure of dichlorobis(pentamethyl-η5-cyclopentadienyl)uranium(IV) and dichlorobis(pentamethyl-η5-cyclopentadienyl)thorium(IV)

“…1 For the Th complex, C atoms were refined isotropicaUy. (4) CI--An--C1 97.9 (4) 100.1 ( (Fagan et al, 1980). The U---C1 bond length, 2.583 (6)A, is quite close to that of 2.638 (4) A observed in UC14 (Taylor & Wilson, 1973) 1.…”

“…The An--C distances ( (Fagan et al, 1980). The angles Cp--An--Cp (where Cp = ring centroid) are in both cases much larger than the angle C1--An--CI, presumably as a result of intramolecular contact of methyl groups.…”

Thermochemical Considerations of Metal Enolates

“…Cp* 2 Th(Cl)(C(O)CH 2 Bu-t) with an anionic acyl group that readily rearranges to the isomeric enolate Cp* 2 Th(Cl)OCH=CHBu-t. The Zisomer is formed upon heating 154 and the E-isomer upon catalysis with Cp* 2 ThH 2 155 . Is the E or Z enolate thermodynamically more stable?…”

Actinide Organometallic Chemistry

“…32) to yield, quantitatively, cisbutenediolate complexes (54,56). In effect, four CO molecules With bulkier hydrocarbyl functionalities, the carbon-carbon fusion is found to be intramolecular (43).…”

“…5) (56); Eq. 34 shows a tentative mechanism which is supported by model studies with alkyl isocyanides.…”