Synthesis, structure and reactivity of tert-butyldimethylsilylcyclopentadienyl lanthanide chlorides, including crystal structures of [(C5H4SiMe2But)2Gd(μ-Cl)]2 and (C5H4SiMe2But)2Er(SBT)(THF)

Reactions of anhydrous lanthanide trichloride with one or two equivalent of tert-butyldimethylsilylcyclopentadienyl (Cp') potassium salt in THF afford mono(tert-butyldimethylsilylcyclopentadienyl)lanthanide dichloride complexes Cp'LnCl(2)(THF)(3) [Ln = Y(1), Er(2)] and bis(tert-butyldimethylsilylcyclopentadienyl)lanthanide chlorides [Cp-2'Ln(mu-Cl)](2) [Ln = Gd(3), Er(4), Yb(5)]. respectively. DyCl3 reacts with KCp' in THF, followed by the treatment with two equivalents of C5H5Na to form the mixed-ring complex Cp'Cp2Dy(THF) (6). Reaction of 4 with LiNPr2' and subsequently with one equivalent of PhNCO in THF give the PhNCO insertion product Cp-2'Er[OC(NPr2)NPh](THF) (7). Complex 4 reacts with one equivalent of sodium benzothiazole-2-thiolate (NaSBT) to yield Cp-2'Er(SBT)(THF) (8). Complexes 1-8 have been characterized by elemental analyses, infrared. H-1-NMR and mass spectroscopies. The molecular structures of 3 and 8 were determined by single crystal X-ray diffraction. 2002 Published by Elsevier Science B.V.