Effects of methyl substituents at the cyclopentadienyl ligand on the properties of C5H5TiCl3 and C5H5TiAl2Cl8-x(C2H5)x (x = 0–4) complexes

摘要: Abstract The methyl substituents in the series of C pTiCl3 compounds ( P = Cp, MeCp, Me3Cp, Me4Cp, Me5 Cp and EtMe4Cp) shift position their CT absorption band from λ 384 nm to max. 438 decrease rate reduction by ethylaluminium yielding trinuclear pTiAl2Cl8 - xEtx (x 0–4) complexes. In pTiCl3/excess Et2AlCl systems was controlled pseudomonomolecular decomposition proposed octahedral intermediate pTiEt(Cl2AlEt2)(Cl3AlEt). constants for decreased above 1.10 × 10−3 6.15 10−5 s−1. pTiAl2Cl8-xEtx complexes shifted charge transfer bands longer wavelengths, d-d transition shorter wavelengths ESR g-value away free electron value. opposite shifts were induced replacement outer chlorine atoms chloroaluminate ligands ethyl groups. On going Me5Cp thermal stability while pTiAl2Cl4Et4 became stable even with excess Et3Al. also formed redox reaction non-dimerizing methylcyclopentadienes (Me3CpH/EtMe4CpH) bis(di-μ-chloroalane)(benzene)titanium(II) C6H6 · TiAl2Cl8-xEtx 0–2). found stoichiometric except perchloro forming diamagnetic byproducts.