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Synthesis, structural characterisation and solution behaviour of high-symmetry lanthanide triflate complexes with the sterically demanding phosphine oxides Cy3PO and tBu3PO

Synthesis, structural characterisation and solution behaviour of high-symmetry lanthanide triflate complexes with the sterically demanding phosphine oxides Cy3PO and tBu3PO
Synthesis, structural characterisation and solution behaviour of high-symmetry lanthanide triflate complexes with the sterically demanding phosphine oxides Cy3PO and tBu3PO
The synthesis and characterisation of complexes formed from lanthanide trifluoromethanesulfonates [Ln(OTf)3] and tricyclohexylphosphine oxide (Cy3PO) or tri-tert-butylphosphine oxide (tBu3PO) are described. The structures of [Ln(H2O)5(Cy3PO)2]·2R3PO·(OTf)3 (Ln = Pr, Tm; R = Cy and Ln = Nd; R = tBu) are pentagonal bipyramidal with an equatorial plane of five H2O ligands and two axial Cy3PO ligands. The remaining Cy3PO molecules are H-bonded to the coordinated water molecules, as are the triflate anions. NMR spectroscopy showed that the triflate ions remain associated with the complexes in CDCl3 solution. Lanthanide-induced shifts in the 19F and 31P NMR spectra confirm that one structure is present for all the lanthanides with an additional structure for the heavier metals. The acidity of the complexes was examined by 31P NMR spectroscopic studies on the reactions between [Ln(H2O)5(Cy3PO)2]·2Cy3PO·(OTf)3 (Ln = La, Eu, Er, Lu) and phosphines PR3 (R = Ph, mesityl, Cy), Ph2PC2H4PPh2 and Ph2PC3H6PPh2. Protonation of the more basic phosphines and H-bonding to the less basic phosphines is observed.
lanthanides, phosphine oxide ligands, acidity O ligands, hydrogen bonds
1434-1948
1464-1471
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Platt, Andrew W.G.
2148bd66-0f68-4390-a262-e57ac72f52f2
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Platt, Andrew W.G.
2148bd66-0f68-4390-a262-e57ac72f52f2

Coles, Simon J., Pitak, Mateusz B. and Platt, Andrew W.G. (2017) Synthesis, structural characterisation and solution behaviour of high-symmetry lanthanide triflate complexes with the sterically demanding phosphine oxides Cy3PO and tBu3PO. European Journal of Inorganic Chemistry, 2017 (11), 1464-1471. (doi:10.1002/ejic.201601471).

Record type: Article

Abstract

The synthesis and characterisation of complexes formed from lanthanide trifluoromethanesulfonates [Ln(OTf)3] and tricyclohexylphosphine oxide (Cy3PO) or tri-tert-butylphosphine oxide (tBu3PO) are described. The structures of [Ln(H2O)5(Cy3PO)2]·2R3PO·(OTf)3 (Ln = Pr, Tm; R = Cy and Ln = Nd; R = tBu) are pentagonal bipyramidal with an equatorial plane of five H2O ligands and two axial Cy3PO ligands. The remaining Cy3PO molecules are H-bonded to the coordinated water molecules, as are the triflate anions. NMR spectroscopy showed that the triflate ions remain associated with the complexes in CDCl3 solution. Lanthanide-induced shifts in the 19F and 31P NMR spectra confirm that one structure is present for all the lanthanides with an additional structure for the heavier metals. The acidity of the complexes was examined by 31P NMR spectroscopic studies on the reactions between [Ln(H2O)5(Cy3PO)2]·2Cy3PO·(OTf)3 (Ln = La, Eu, Er, Lu) and phosphines PR3 (R = Ph, mesityl, Cy), Ph2PC2H4PPh2 and Ph2PC3H6PPh2. Protonation of the more basic phosphines and H-bonding to the less basic phosphines is observed.

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Accepted/In Press date: 1 December 2016
e-pub ahead of print date: 25 January 2017
Published date: 17 March 2017
Keywords: lanthanides, phosphine oxide ligands, acidity O ligands, hydrogen bonds
Organisations: Chemistry, Chemistry Research Support

Identifiers

Local EPrints ID: 410773
URI: http://eprints.soton.ac.uk/id/eprint/410773
ISSN: 1434-1948
PURE UUID: 3693fd2c-9497-4a29-92f5-4ccc2dbcc6d5
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Mateusz B. Pitak: ORCID iD orcid.org/0000-0002-3680-7100

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Date deposited: 09 Jun 2017 09:37
Last modified: 18 Feb 2021 16:53

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Contributors

Author: Simon J. Coles ORCID iD
Author: Mateusz B. Pitak ORCID iD
Author: Andrew W.G. Platt

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