A Rare-Earth-Metal Ensemble of the Tebbe Reagent: Scope of Coligands and Carbonyl Olefination

Treatment of the half-sandwich complexes Cp(R)Ln-(AlMe4)(2) (Cp-R = C5Me5, C5Me4SiMe3; Ln = Y, La, Lu) with the mild halogenido transfer reagents SiMe3X (X = Cl, Br, I) resulted in efficient and selective halogenido/tetramethylaluminato exchange. Depending on the size of the rare-earth metal, dimeric [Cp(R)Ln(AlMe4)(mu-X)](2) (Ln = Y, Lu) and decametallic [(Cp3La3)-La-R(AlMe4)(2)(mu-X)(4)](2) could be obtained. Donor (THF)-induced tetramethylaluminato cleavage gave access to methyl-free mixed methylidene/halogenido complexes Cp(3)(R)Ln(3)(mu-X)(3)(mu(3)-X)(mu(3)-CH2)(THF)(3) for yttrium (X = Cl, Br) and lanthanum (X = Cl, Br, I) in good yields. Additionally, mixed methylidene/halogenido Y(III) complexes could be obtained via methyl/halogenido exchange employing (C5Me5)(3)Y-3(mu-Me)(3)(mu(3)-Me)(mu(3)-CH2)(THF)(2) and SiMe3X via tetramethylsilane elimination. All methylidene complexes were probed in olefination reactions and found to act as efficient Schrock-type nucleophilic carbenes converting ketones and aldehydes into the respective terminal alkenes. Such reactivity is as high as that of the prominent Tebbe reagent but is less tolerant toward sterically demanding and functionalized substrates (such as esters). In contrast to the Tebbe reagent, complexes CpR(3)Ln(3)(mu-X)(3)(mu(3)-X)(mu(3)-CH2)(THF)(3) polymerize delta-valerolactone in an efficient manner, generating polylactones with molecular weight distributions M-w/M-n as low as 1.13. Moreover, the bromido variant of the Tebbe reagent, Cp2Ti(mu-CH2)(mu-Br)AlMe2, is described, underlying similar synthesis limitations: that is, the coformation (and hence cocrystallization) of the trivalent species Cp2Ti(mu-Br)(2)AlMe2.