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Effects of methyl substituents at the cyclopentadienyl ligand on the properties of C2H5TiCl3 and C5H5TiAl2CL8-x(C2H5)x (x = 0-4) complexes
The methyl substituents in the series of <*>pTiCl3 compounds (<*>p = Cp, MeCp, Me3Cp, Me4Cp, Me5Cp and EtMe4Cp) shift the position of their CT absorption band from lambda = 384 nm to max. 438 nm and decrease the rate of reduction of <*>pTiCl3 by ethylaluminium compounds yielding the trinuclear <*>pTiAl2Cl8-xEtx (x = 0-4) complexes.In the <*>pTiCl3/excess Et2AlCl systems the rate of reduction was controlled by pseudomonomolecular decomposition of the proposed octahedral intermediate <*>pTiEt(Cl2AlEt2)(Cl3AlEt).The rate constants for reduction decreased in the above series of <*>pTiCl3 compounds from 1.10*10-3 to 6.15*10-5 s-1.The methyl substituents in the <*>pTiAl2Cl8-xEtx complexes shifted the charge transfer bands to longer wavelengths, the d-d transition to shorter wavelengths and the ESR g-value away from the free electron value.The opposite shifts were induced by the replacement of the outer chlorine atoms in the chloroaluminate ligands by ethyl groups.On going from Cp to Me5Cp the thermal stability of the <*>pTiAl2Cl8 complexes decreased while the complexes <*>pTiAl2Cl4Al4 became stable even with the excess of Et3Al.The <*>pTiAl2Cl8-xEtx complexes were also formed in the redox reaction of non-dimerizing methylcyclopentadienes (Me3CpH/EtMe4CpH) with bis(di-mu-chloroalane)(benzene)titanium(II) complexes C6H6*TiAl2Cl8-xEtx (x = 0-2).The reaction was found stoichiometric except for the perchloro complexes forming diamagnetic byproducts.
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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI