"Ionic carbenes": synthesis, structural characterization, and reactivity of rare-Earth metal methylidene complexes

H Martin Dietrich; Karl W Törnroos; Reiner Anwander

doi:10.1021/ja062523y

"Ionic carbenes": synthesis, structural characterization, and reactivity of rare-Earth metal methylidene complexes

J Am Chem Soc. 2006 Jul 26;128(29):9298-9. doi: 10.1021/ja062523y.

Authors

H Martin Dietrich¹, Karl W Törnroos, Reiner Anwander

Affiliation

¹ Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway.

PMID: 16848442
DOI: 10.1021/ja062523y

Abstract

Treatment of mixed chloride tetramethylaluminate polynuclear clusters {Cp*Y[(mu-Me)2AlMe2](mu-Cl)}2 and {Cp*6La6[(mu-Me)3AlMe]4(mu3-Cl)2(mu2-Cl)6} with toluene/THF solutions produces "aluminum-free" methylidene complexes [Cp*3Ln3(mu-Cl)3(mu3-Cl)(mu3-CH2)(THF)3] (Ln = Y, La). The trinuclear methylidene complexes are isostructural in the solid state and feature a sterically well-shielded Schrock-type nucleophilic CH22- unit, which is prone to Tebbe-like methylenation reactions with ketones and aldehydes. The rapid polymerization of gamma-valerolactone reveals intrinsic rare-earth metal reactivity.