title: Formation of a bridging planar trimethylenemethane dianion from a neopentyl precursor via sequential beta-alkyl elimination and C-H activation.
abstract: The reaction of neopentyllithium, Me3CCH2Li, with [(C5Me5)2Sm][(mu-Ph)2BPh2], 1, was investigated as a route to the unsolvated alkyl, [(C5Me5)2Sm(CH2CMe3)]x, and found to generate the first f element trimethylenemethane dianion complex, [(C5Me5)2Sm]2[mu-eta3:eta3-C(CH2)3], 2. Formation of the [C4H6]2- trimethylenemethane ligand from the [C5H11]1- neopentyl precursor can be explained by a combination of a beta-methyl elimination reaction to form isobutene and [(C5Me5)2SmMe]3, 3, with subsequent C-H activation reactions. This sequence has been modeled in several ways, including the synthesis of 2 from reactions of 3 with CH2=CMe2 and 3 with the 2-methylallyl complex, (C5Me5)2Sm[CH2C(Me)CH2], 4.
authors.affiliation: Department of Chemistry, University of California-Irvine, Irvine, California 92697-2025, USA. wevans@uci.edu
authors.forename: William J
authors.initials: WJ
authors.lastname: Evans
authors.forename: Jeremy M
authors.initials: JM
authors.lastname: Perotti
authors.forename: Joseph W
authors.initials: JW
authors.lastname: Ziller