Preparation of Diamidochloro(cyclopentadienyl)titanium Derivatives as Pre-Catalysts for Olefin Polymerization - X-ray Molecular Structure of [Ti(Ti5-C_5H_5){l,2-C_6H_4(NCH_2CH_2CH_3)_2}Cl] and [Ti{eta~5-C_5H_4(SiMe_3)}-{1,2-C_6H_4(NCH_2CH_2CH_3)_2}C1

摘要

The synthesis of N,N'-alkyl 1,2-phenylenediamines 1,2-C_6H_4(NHR)_2 [R = CH_2CH_2CH_3 (nPr),CH_2tBu (Np)] was carried out in three steps by lithiation of the primary 1,2-pheny-lenediamine,reaction with the appropriate acyl chloride and reduction with LiAlH4.The addition of nBuLi to a stirred solution of JV,N'-alkyl diamines in cold hexane resulted in the immediate deposition of the corresponding lithium salts,which react with [MCp~(R')Cl)3] to give the diamidochloro(eta~5-cyclopentadienyljtitanium and -zirconium complexes [MCp~(R'){l,2-C_6H_4(NR)_2}Cl] (4-10) [M - Ti,Zr;Cp~(R') = eta~5-C_5H_5,ri5-C_5(CH_3)_5,eta~5-C_5H_4(SiMe_3);R = nPr,Np].The compound[Ti(eta~5-C_5H_5){l,2-C_6H_4(NnPr)_2)Cl] (3) was obtained by treatment of [Ti(eta~5-C_5H_5)Cl_3] with l,2-C_6H_4(NHnPr)_2 in the presence of NEt_3 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.