Synthesis And Crystal Structure Of Organolithium And Ansa-Organolanthanide Complexes Involving Substituted Undenyl Ligands

All experiments were performed under an atmosphere of dry argon with the rigid exclusion of air and moisture using standard Schlenk techniques . Reaction of Ar-MgBr with 2-indanone in diethyl ether produced 2-Ar-Ind. Interaction of (2-Ar-Ind)Li with 1/2 equiv of Me2SiCl2 inEt^ resulted in Me2Si(2-Ph-Ind)2 (Al) and Me2[2-(p-Bu1-) Ph-Ind]2 (A2). These compounds were characterized by 'H NMR and 13C NMR. Recrystallization of [2-(p-Bul-)Ph-Ind]Li from Et2O , gave [2-(p-Bu'-)ph-md]Li (Et2O)2 (A3). Treatment of (Al) with 2 equiv of n-BuLi in Et,O produced, after recrystallization , [Me'2Si(2-ph-md)2] Li2 (EtO (A4) in 79% yield. Reaction of (A4) with 1 equiv of anhydrous YC13 in EtjO produced , after recrystallization, [Me2Si(2-ph-md)2] Y( u -Cl)2 Li (Et2O)2 (A5) in 39% yield. Reaction of (A4) with 1 equiv of anhydrous ErCl3 in refluxed THF produced, after recrystallization from toluene and THF, [Me2Si(2-ph-Ind)2]Er( u -Cl)2Li (THF)2 (A6) in 24% yield. Reaction of (A4) with 1 equiv of anhydrous LnCl3 in refluxed THF produced, after recrystallization from hot toluene, [Me2Si(2-ph-Ind)2]Ln( u -Cl)2 Li (THF)2 [Ln=Gd(A7),Yb(A8),Nd(A9), Sm(lOA)]. (A3)-(A10) were fully characterized by MS, IR and elemental analysis. (A3)-(A6) were also determined by X-ray diffraction. In the structures of (A3)-(A6) Li , Y or Er atoms coordinate to five-memerbed rings in n 5-fashion.