The University of Southampton
University of Southampton Institutional Repository

Hard/soft interactions in early transition metal chemistry: synthesis, properties and structures of thioether and selenoether complexes of titanium(IV)

Levason, W., Patel, B., Reid, G., Tolhurst, V. A. and Webster, M. (2000) Hard/soft interactions in early transition metal chemistry: synthesis, properties and structures of thioether and selenoether complexes of titanium(IV) Journal of the Chemical Society-Dalton Transactions, (17), pp. 3001-3006. (doi:10.1039/b002792h).

Record type: Article

Abstract

Reaction of TiCl4 with L-L [L-L=MeE(CH2)(n)EMe; E=S or Se, n=2 or 3, PhE(CH2)(2)EPh or o-C6H4(EMe)(2)] in anhydrous n-hexane solution under an N-2 atmosphere results in the rapid formation of [TiCl4(L-L)] as yellow, orange or red solids. Analogous bromo and iodo species, [TiX4(L-L)] [X=Br; L-L=MeE(CH2)(n)EMe or o-C6H4(EMe)(2); X=I; L-L=MeSe(CH2)(2)SeMe or o-C6H4(SeMe)(2)], were obtained as intense orange or red coloured solids by treatment of TiX4 with L-L in CH2Cl2 solution. Crystallographic studies on [TiCl4{MeS(CH2)(2)SMe}], [TiCl4{MeS(CH2)(3)SMe}], [TiCl4{MeSe(CH2)(3)SeMe}] and [TiCl4{o-C6H4(SeMe)(2)}] reveal a distorted octahedral arrangement with the coordinated group 16 donor ligand adopting the DL form in the first three cases and the meso form in the fourth example. These studies also reveal a trans influence series of Cl > S approximate to Se on Ti(IV). Solution NMR studies show that the chloro-compounds undergo rapid pyramidal inversion at ambient temperature, while the bromo and iodo species also undergo rapid ligand dissociation/chelate ring-opening. At low temperature these processes are slowed significantly, such that in most of the chloro and bromo species it is possible to identify both the meso and DL invertomers, although ligand exchange is still rapid at 200 K for the iodo species. The potential of these compounds as sources of titanium sulfide or titanium selenide phases via controlled decomposition is also discussed briefly. Finally, the dinuclear species, [Cl3Ti{MeS(CH2)(2)SMe}](2)(mu-O), formed by partial hydrolysis of [TiCl4{MeS(CH2)(2)SMe}], has also been identified crystallographically.

Full text not available from this repository.

More information

Published date: 2000
Keywords: nuclear-magnetic-resonance, neutral lewis-bases, tin(iv) halides, dithioether complexes, molecular-structures, crystal-structures, adducts, ligands, tetrachloride, tetrahalides

Identifiers

Local EPrints ID: 19014
URI: http://eprints.soton.ac.uk/id/eprint/19014
PURE UUID: 31d41b9b-8052-44e0-83b6-f4ec3c7f8302

Catalogue record

Date deposited: 20 Dec 2005
Last modified: 17 Jul 2017 16:34

Export record

Altmetrics

Contributors

Author: W. Levason
Author: B. Patel
Author: G. Reid
Author: V. A. Tolhurst
Author: M. Webster

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×