Organometallic Compounds of the Lanthanides. 128.1Donor-Functionalized Chiral Nonracemic Cyclopentadienyl Complexes of Yttrium, Samarium(III), and Lutetium

Abstract

Optically active metallocene complexes of Y, Sm(III), and Lu containing cyclopentadienyl ligands with chiral nonracemic N- or O-substituted side chains as ligands are described. Specifically, the ligand systems reported are (S)-(2-methoxypropyl)cyclopentadienyl [(S)-C5H4CH2CH(Me)OMe)], (S)-[2-(dimethylamino)propyl]cyclopentadienyl [(S)-C5H4CH2CH(Me)NMe2)], and (S)-[2-(dimethylamino)-1-(phenylethyl)]cyclopentadienyl [(S)-C5H4CH(Ph)CH2NMe2)]. Reaction of the potassium salts of these cyclopentadienyl systems with the trichlorides of Y, Sm, and Lu in a 2:1 molar ratio yielded the complexes [Ln{(S)-η5:η1-C5H4(CH2CH(Me)OMe)}2Cl] (Ln = Y 1a, Sm 1b), [Ln{(S)-η5:η1-C5H4[CH2CH(Me)NMe2]}2Cl] (Ln = Y 2a, Sm 2b), and [Ln{(S)-η5:η1-C5H4[CH(Ph)CH2NMe2]}2Cl] (Ln = Y 3a, Sm 3b, Lu 3c). Alternatively, 2b was synthesized by oxidation of the corresponding divalent complex [Sm{(S)-η5:η1-C5H4[CH2CH(Me)NMe2]}2] with tert-butyl chloride. The mixed chiral sandwich complexes [(η5-C5Me5)Ln{(S)-η5:η1-C5H4[CH2CH(Me)NMe2]}Cl] (Ln = Y ...