Fluorenyl and ansa-Dimethylsilylbis(fluorenyl) Derivatives of Divalent Ytterbium and Samarium - Synthesis and Structure of the First Mixed-Ligand Ln~(II) Classic Sandwich Complex (C_(13)H_9)(C_5Me_5)Yb(DME)

摘要

Novel fluorenyl complexes of divalent ytterbium (C_(13)H_9)_2Yb(L)_n [L = THF, n = 2 (1); L = DME, n = 1 (2)] have been prepared by reaction of YbI_2(THF)_2 with 2 equiv. of C_(13)H_9K as well as by reaction of (C_(10)H_8)Yb(THF)_2 with fluorene in THF. Oxidation of 1 by tBuN=CHCN=NtBu (DAD) resulted in the formation of (C_(13)H_9)_2 Yb(DAD) (3). The reaction of {YbI(DME)_2]_2(μ-C_(10)H_8)} (4) with fluorene did not give (C_(13)H_9)YbI(DME) (5), but the redistribution products YbI_2(DME) and 2. The first mixed-ligand sandwich complex of a divalent lanthanide metal (C_(13)H_9)(C_5Me_5)Yb(DME) (6) was prepared in a one-pot reaction of 4 with C_5Me_5H and C_(13)H_9K in DME, ansa-Me_2Si(C_(13)H_8)_2Yb(THF) (7) and ansa-Me_2Si(C_(13)H_8)_2Sm(THF)_4 (8) were obtained by treatment of the appropriate Ln~(II) iodides with ansa-Me_2Si(C_(13)H_9)_2K_2 in THF. The molecular structures of 1 and 6 were determined by single-crystal X-ray diffraction.