Synthesis, Molecular Structure, and Reactivity of Organolanthanide Fluoride Complexes, [{(Me3Si)2C5H3}2Ln(μ-F)]2(Ln = La, Nd, Sm, Gd) and [(C5H5)2Ln(μ-F)(THF)]2(Ln = Y, Yb)

Treatment of Me 3 NHF with 1 equiv of [(Me 3 Si) 2 C 5 H 3 ] 3 Ln or (C 5 H 5 ) 3 Ln in THF gave [{(Me 3 Si) 2 C 5 H 3 } 2 LnF] 2 (Ln = La ( 1 ), Nd ( 2 ), Sm ( 3 ), Gd ( 4 )) or [(C 5 H 5 ) 2 LnF(THF)] 2 (Ln = Y ( 5 ), Yb ( 6 )) in moderate to good yield. All of them were fully characterized by elemental analyses, spectroscopy, and X-ray analyses. Compound 3 reacted with Na, AlCl 3, (C 6 H 5 ) 3 SiOH, and 2,6-Pr i 2 C 6 H 3 OH to form [(Me 3 Si) 2 C 5 H 3 ] 2 Sm(THF), [{(Me 3 Si) 2 C 5 H 3 } 2 SmCl] 2, [(C 6 H 5 ) 3 SiO] 3 Sm(THF) 3 ( 7 ), and [2,6-Pr i 2 C 6 H 3 O] 3 Sm(THF) 3 ( 8 ), respectively. The molecular structures of [{(Me 3 Si) 2 C 5 H 3 } 2 SmCl] 2, 7, and 8 were confirmed by X-ray diffraction study. The 3 /NaH system can convert C 6 H 5 Br into C 6 H 6 in 32% yield.