UNSPECIFIED (1997) Halide-abstraction reactions of tin(IV) and lanthanide(III) chlorides in tetrahydrofuran: crystal and molecular structures of [LnCl(2)(thf)(5)][SnCl5(thf)] where Ln=Ce, Gd or Yb. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (15). pp. 2677-2680. ISSN 0300-9246

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Abstract

It has been established that halide abstraction from several lanthanide(III) chlorides can be effected by tin tetrachloride. Direct treatment (1: I) of LnCl(3) where Ln = Ce, Gd or Yb with SnCl4 in tetrahydrofuran (thf) provided colourless compounds of the generic type LnSnCl(7)(thf)(6) which have been identified by X-ray crystallography as ionic salts [trans-LnCl(2)(thf)(5)][SnCl5(thf)]. The individual seven-co-ordinate cations feature a regular pentagonal-bipyramidal metal geometry in which a trans-LnCl(2) unit is surrounded by five thf molecules arranged in an equatorial plane. These co-ordinated solvent molecules adopt the familiar 'propeller-like' arrangement indicative of a skew as opposed to envelope ligand conformation. For Ln = Ce, Ce-Cl 2.697(2), Ce-O mean 2.495(5) Angstrom; for Ln = Gd, Gd-Cl 2.608(2), Gd-O mean 2.415(4) Angstrom; for Ln = Yb, Yb-Cl 2.5375(13), Yb-O mean 2.346(4) Angstrom. The six-co-ordinate [SnCl5(thf)](-) anions common to the series show a two-fold axis of symmetry containing the metal atom, the oxygen (thf) atom and a chloride atom mutually trans to the latter. Bond distances for Ln = Ce, i.e. Sn-O 2.276(7), Sn-Cl mean 2.399(2) Angstrom, are typical for the series.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
ISSN:	0300-9246
Date:	7 August 1997
Number:	15
Number of Pages:	4
Page Range:	pp. 2677-2680
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/16488

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