Preparation of Diamidochloro(cyclopentadienyl)titanium Derivatives as Pre‐Catalysts for Olefin Polymerization − X‐ray Molecular Structure of [Ti(η5‐C5H5){1,2‐C6H4(NCH2CH2CH3)2}Cl] and [Ti{η5‐C5H4(SiMe3)}{1,2‐C6H4(NCH2CH2CH3)2}Cl

Abstract

AbstractThe synthesis of N,N′‐alkyl 1,2‐phenylenediamines 1,2‐C6H4(NHR)2 [R = CH2CH2CH3 (nPr), CH2tBu (Np)] was carried out in three steps by lithiation of the primary 1,2‐phenylenediamine, reaction with the appropriate acyl chloride and reduction with LiAlH4. The addition of nBuLi to a stirred solution of N,N′‐alkyl diamines in cold hexane resulted in the immediate deposition of the corresponding lithium salts, which react with [MCpR′Cl3] to give the diamidochloro(η5‐cyclopentadienyl)titanium and ‐zirconium complexes [MCpR′{1,2‐C6H4(NR)2}Cl] (4−10) [M = Ti, Zr; CpR′ = η5‐C5H5, η5‐C5(CH3)5, η5‐C5H4(SiMe3); R = nPr, Np]. The compound [Ti(η5‐C5H5){1,2‐C6H4(NnPr)2}Cl] (3) was obtained by treatment of [Ti(η5‐C5H5)Cl3] with 1,2‐C6H4(NHnPr)2 in the presence of NEt3 in toluene. All the reported compounds were characterized by the usual analytical and NMR spectroscopic methods. The molecular structures of 3 and 7 were determined by single‐crystal X‐ray crystallography. The compounds described here were further investigated as potential olefin polymerization catalysts. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)