Organometallic Compounds of the Lanthanides. 128.1Donor-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 )-C 5 H 4 CH 2 CH(Me)OMe)], ( S )-[2-(dimethylamino)propyl]cyclopentadienyl [( S )-C 5 H 4 CH 2 CH(Me)NMe 2 )], and ( S )-[2-(dimethylamino)-1-(phenylethyl)]cyclopentadienyl [( S )-C 5 H 4 CH(Ph)CH 2 NMe 2 )]. 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 )-η 5:η 1 -C 5 H 4 (CH 2 CH(Me)OMe)} 2 Cl] (Ln = Y 1a, Sm 1b ), [Ln{( S )-η 5:η 1 -C 5 H 4 [CH 2 CH(Me)NMe 2 ]} 2 Cl] (Ln = Y 2a, Sm 2b ), and [Ln{( S )-η 5:η 1 -C 5 H 4 [CH(Ph)CH 2 NMe 2 ]} 2 Cl] (Ln = Y 3a, Sm 3b, Lu 3c ). Alternatively, 2b was synthesized by oxidation of the corresponding divalent complex [Sm{( S )-η 5:η 1 -C 5 H 4 [CH 2 CH(Me)NMe 2 ]} 2 ] with tert -butyl chloride. The mixed chiral sandwich complexes [(η 5 -C 5 Me 5 )Ln{( S )-η 5:η 1 -C 5 H 4 [CH 2 CH(Me)NMe 2 ]}Cl] (Ln = Y 4a, Lu 4c ) and [(η 5 -C 5 Me 5 )Ln{( S )-η 5:η 1 -C 5 H 4 [CH(Ph)CH 2 NMe 2 ]}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(C 5 Me 5 ). Methylation of 5c with LiMe produced [(η 5 -C 5 Me 5 )Ln{( S )-η 5:η 1 -C 5 H 4 [CH(Ph)CH 2 NMe 2 ]}Me] ( 6c ). X-ray structural analyses of 1b, 3b, 3c, 5a, and 6c were performed.