Neodymium(<scp>II</scp>) and Dysprosium(<scp>II</scp>) Iodides in the Reactions with Metallocenes of d‐Transition Metals

Abstract

Abstract Heating NdI 2 ( 1 ) or DyI 2 ( 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 CpLnI 2 (THF) 3 after crystallization from THF. The interaction of 2 with 3 in isopropylbenzene at 90 °C yielded a mixture of (arene) 2 V 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 ] 7 Cp 2 V(μ‐I)}( 4 ) was isolated in low yield. The reaction of Cp 2 Cr with 1 or 2 in benzene at ambient temperature afforded the dimer [CpCr(μ‐I)] 2 ( 5 ) and a dysprosium complex, Cp 2 DyI ( 6 ) (in the reaction with 2 ). When the reaction with 2 was carried out at 80 °C, along with compound 6 , the ‐ate complex {[Cp 2 DyI 2 ] – [Cp 2 Cr] + }( 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 &amp; Co. KGaA, 69451 Weinheim, Germany, 2006)