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 cyc lopentadienyl ligands with chiral nonracemic N- or O-substituted side chain s as ligands are described. Specifically, the ligand systems reported are ( S)-(2-methoxypropyl)cyclopentadienyl [(S)-C5H4CH2CH(Me)OMe)], (S)-[2-(dimet hylamino)propyl]cyclopentadienyl [(S)-C5H4CH2CH(Me)NMe2)], and (S)-[2-(dime thylamino)-1-(phenylethyl)]cyclopentadienyl [(S)-C5H4CH(Ph)CH2NMe2)]. React ion of the potassium salts of these cyclopentadienyl systems with the trich lorides 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):e ta(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 mix ed 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)-C 5H4[CH(Ph)CH2NMe2]}Cl] (Ln = Y 5a, Lu 5c) were prepared by successive react ion of the lanthanide trichlorides with 1 equiv of the potassium salt of th e chiral nonracemic cyclopentadienyl ligand and 1 equiv of Na(C5Me5). Methy lation 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 w ere performed.