The University of Southampton
University of Southampton Institutional Repository

Tetrakis(triphenylphosphine oxide) complexes of the lanthanide nitrates; synthesis, characterisation and crystal structures of La(Ph3PO)(4)(NO3)(3) center dot Me2CO and Lu(Ph3PO)(4)(NO3)(2) NO3

Record type: Article

The reaction of Ln(NO3)(3). 6H(2)O (Ln = La, Ce, Pr or Nd) with a sixfold excess of Ph3PO in acetone formed [Ln(Ph3PO)(4)(NO3)(3)]. Me2CO. The crystal structure of the La complex shows a nine-coordinate metal centre with four phosphine oxides, two bidentate and one monodentate nitrate groups, and PXRD studies show the same structure is present in the other three complexes. In CH2Cl2 or Me2CO solutions, P-31 NMR studies show that the complexes are essentially completely decomposed into [Ln(Ph3PO)(3)(NO3)(3)] and Ph3PO. Similar reactions in ethanol gave [Ln(Ph3PO)(3)(NO3)(3)] only. In contrast for Ln = Sm, Eu or Gd. only the [Ln(Ph3PO)(3)(NO3)(3)] are formed from either acetone or ethanol solutions. For the later lanthanides Ln = Tb-Lu, acetone solutions of Ln(NO3)(3). 6H(2)O and Ph3PO gave [Ln(Ph3PO)(3)(NO3)(3)] only, even with a large excess of Ph3PO, but from cold ethanol [Ln(Ph3PO)(4)(NO3)(2)]NO3 (Ln = Tb, Ho-Lu) were obtained. The structure of [Lu(Ph3PO)(4)(NO3)(2)]NO3 shows an eight-coordinate metal centre with four phosphine oxides and two bidentate nitrate groups. In solution in CH2Cl2 or Me2CO the tetrakis-complexes show varying amounts of decomposition into mixtures of [Ln(Ph3PO)(3)(NO3)(3)]. [Ln( Ph3PO)(4)(NO3)(2)]NO3 and Ph3PO as judged by P-31{H-1} NMR spectroscopy. The [Ln(Ph3PO)(3)(NO3)(3)] also partially decompose in solution for Ln = Dy-Lu. forming some tetrakis(phosphine oxide) species.

Full text not available from this repository.

Citation

Levason, W., Newman, E. H. and Webster, M. (2000) Tetrakis(triphenylphosphine oxide) complexes of the lanthanide nitrates; synthesis, characterisation and crystal structures of La(Ph3PO)(4)(NO3)(3) center dot Me2CO and Lu(Ph3PO)(4)(NO3)(2) NO3 Polyhedron, 19, (28), pp. 2697-2705. (doi:10.1016/S0277-5387(00)00588-X).

More information

Published date: 30 December 2000
Keywords: lanthanides, phosphine oxides, x-ray structures

Identifiers

Local EPrints ID: 18855
URI: http://eprints.soton.ac.uk/id/eprint/18855
ISSN: 0277-5387
PURE UUID: f60cde7e-1723-472a-9fa1-c54650a16625

Catalogue record

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

Export record

Altmetrics

Contributors

Author: W. Levason
Author: E. H. Newman
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.

×