Stereoselective formation of ansa-metallocenes in reactions of radical-anionic salts of acenaphthylene with lanthanide and calcium halides

Abstract

ansa-Metallocenes (η5:η5-C24H16)M(THF)2 (M = Sm (1), Yb (2), Ca (3)) and (η5:η5-C24H16)MI(THF) (M = Dy (8), Er (9), Tm (10), Lu (11)) were prepared in 50—90% yields by the in situ reactions of two equivalents of potassium acenaphthylenide K+C12H8– with MI2 or MI3, respectively. Complexes 2 and 3 were also obtained by direct reduction of acenaphthylene with ytterbium and calcium naphthalenides, respectively. An ESR signal of the acenaphthylene radical anion, which was observed upon dissolution of compound 2 in THF, indicates that the [C24H16]2–ansa-ligand dissociated into two [C12H8]·– radical anions. Hydrolysis of complex 2 in benzene afforded 1,1",3,3"-tetrahydro-3,3"-biacenaphthylene (4) and 3,3",4,4"-tetrahydro-3,3"-biacenaphthylene (5). The reaction of complex 2 with ZrCl4 and the reaction of compound 3 with Me3SiCl proceeded with the cleavage of the C—C bond between two acenaphthylene fragments of the [C24H16]2–ansa-ligand to produce (η2-C12H8)ZrCl2(THF)3 (6) and bis(trimethylsilyl)acenaphthene (Me3Si)2C12H8 (7), respectively. Compounds 1—3, 6, 7, and 11 were characterized by 1H and 13C NMR spectroscopy. The temperature dependence of the 1H NMR spectrum of compound 11 in tetrahydrofuran is indicative of the dynamic exchange of the solvent molecules in the coordination sphere of the Lu atom. After cooling of the solution to 210 K, the dynamic process was terminated as evidenced by the nonequivalence of the 1H signals of two acenaphthylene fragments. According to the X-ray diffraction data for complex 11, dimerization of two acenaphthylene radical anions at the Lu atom gave rise to the rac-ansa-metallocene structure. In compound 11, the Lu atom is η5-coordinated by two five-membered rings of the acenaphthylene ligands and also by the I atom and the THF molecule. The coordination environment about the Lu atom is a distorted tetrahedron. The average distance between the lutetium atom and the carbon atoms of the five-membered rings is 2.623 A.