Organometallic compounds of the lanthanides. 128. Donor functionalized chiral nonracemic cyclopentadienyl complexes of yttrium, samarium(III), and lutetium

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)-eta(5):eta(1)-C5H4(CH2CH(Me)OMe)}(2)Cl] (Ln = Y 1a, Sm 1b), [Ln{(S)-eta(5):eta(1)-C5H4[CH2CH(Me)NMe2]}(2)Cl] (Ln = Y 2a, Sm 2b), and [Ln{(S)-eta(5):eta(1)-C5H4[CH(Ph)CH2NMe2]}(2)Cl] (Ln = Y 3a, Sm 3b, Lu 3c). Alternatively, 2b was synthesized by oxidation of the corresponding divalent complex [Sm{(S)-eta(5):eta(1)-C5H4[CH2CH(Me)NMe2]}(2)] with tert-butyl chloride. The mixed chiral sandwich complexes [(eta(5)-C5Me5)Ln{(S)-eta(5):eta(1)-C5H4[CH2CH(Me)NMe2]}Cl] (Ln = Y 4a, Lu 4c) and [(eta(5)-C5Me5)Ln{(S)-eta(5) :eta(1)-C5H4[CH(Ph)CH2NMe2]}Cl] (Ln = Y 5a, Lu 5c) were prepared by successive reaction of the lanthanide trichlorides with 1 equiv of the potassium salt of the chiral nonracemic cyclopentadienyl ligand and 1 equiv of Na(C5Me5). Methylation of 5c with LiMe produced [(eta(5)-C5Me5)Ln{(S)-eta(5):eta(1)-C5H4[CH(Ph)CH2NMe2]}Me] (6c) X-ray structural analyses of 1b, 3b, 3c, 5a, and 6c were performed.