Neodymium(II) and Dysprosium(II) Iodides in the Reactions with Metallocenes of d-Transition Metals

Heating NdI2 (1) or DyI2 (2) with vanadocene (3) in benzene at 85 °C led to the formation of bis(benzene)vanadium in 10 and 24 % yields, respectively. The lanthanide products were isolated in the form of CpLnI2(THF)3 after crystallization from THF. The interaction of 2 with 3 in isopropylbenzene at 90 °C yielded a mixture of (arene)2V complexes from which a small amount of bis(isopropylbenzene)vanadium was isolated. The same reaction did not occur in mesitylene. From the reaction of 2 with 3 in molten naphthalene at 100 °C, the heterobimetallic cluster {[CpDy(μ-I)2]7Cp2V(μ-I)}(4) was isolated in low yield. The reaction of Cp2Cr with 1 or 2 in benzene at ambient temperature afforded the dimer [CpCr(μ-I)]2 (5) and a dysprosium complex, Cp2DyI (6) (in the reaction with 2). When the reaction with 2 was carried out at 80 °C, along with compound 6, the -ate complex {[Cp2DyI2]–[Cp2Cr]+}(7) was crystallized from the reaction solution. Nickelocene was reduced by 2 in benzene at 80 °C to nickel metal. The dysprosium product was isolated as solvent-free complex 6. Ferrocene and cobaltocene did not react with 1 and 2 in benzene. The molecular structures of compounds 4, 5, and 7 were characterized by X-ray diffraction analysis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)