Cationic titanium(IV) complexes via halide abstraction from [Ti(C5H5)Cl3]: crystal and molecular structure of [Ti(C5H5)(MeCN)5SbCl63].2MeCN

Willey, Gerald R. and Butcher, Mark L. and McPartlin, Mary and Scowen, Ian J. (1994) Cationic titanium(IV) complexes via halide abstraction from [Ti(C5H5)Cl3]: crystal and molecular structure of [Ti(C5H5)(MeCN)5SbCl63].2MeCN. Journal of the Chemical Society, Dalton Trans. (3). pp. 305-309. ISSN 1477-9226, 1470-479X

Full content URL: http://dx.doi.org/10.1039/DT9940000305

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Item Type:Article
Item Status:Live Archive

Abstract

Treatment of Ti(cp)Cl(cp =small eta-CH) with SbCl as chloride abstractor in acetonitrile provided hexachloroantimonate() salts of Ti(cp)Cl{,} Ti(cp)Cl and Ti(cp) respectively. With 1 : 1 stoichiometry red-brown crystals of Ti(cp)Cl(MeCN)SbCl are obtained and with 1 : 2 stoichiometry light blue crystals of Ti(cp)Cl(MeCN)SbCl. Complete removal of chloride ion from Ti(cp)Cl requires a six-fold excess of SbCl when purple-blue crystals of Ti(cp)(MeCN)SbCl can be isolated. These products were characterised by analytical and spectroscopic (IR{,} H NMR) data and{,} in the case of {,} by a crystal structure determination. Proton NMR studies indicate the presence of intermediate halide-bridged Ti(small micro]-Cl)Sb] species in solution during the sequential halide abstractions rightward arrowrightward arrow. Crystals of complex {,} obtained as the bis(solvate) from recrystallisation in acetonitrile{,} are monoclinic and X-ray structural analysis confirmed the formulation. The crystal structure space group {,} = 19.650(4){,} = 19.182(4){,} = 12.958(3)A{,} small beta]= 91.612(3)degree{,} = 4{,} = 0.0386{,} prime or minute= 0.0406 shows discrete cations and anions and a pseudo-octahedral co-ordination sphere for the Ti. A significant influence of the cyclopentadienyl ligand affects Ti-N bond lengths in the complex.

Keywords:Chemistry
Subjects:F Physical Sciences > F100 Chemistry
Divisions:College of Science > School of Chemistry
ID Code:13264
Deposited On:19 Mar 2014 17:51

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