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Complexes of lanthanide nitrates with tri tert butylphosphine oxide

Complexes of lanthanide nitrates with tri tert butylphosphine oxide
Complexes of lanthanide nitrates with tri tert butylphosphine oxide
Reaction of lanthanide nitrates with (Bu3PO)-Bu-t (=L) lead to the isolation of complexes Ln(NO3)(3)L-2 center dot H2O center dot nEtOH (Ln = La (1), Nd(2)), Ln(NO3)(3)L-2 center dot nEtOH (Sm(3), Eu(4)), and Ln(NO3)(3)L-2 (Dy(5), Er(6), Lu(7)). These have been characterized by elemental analysis, infrared and NMR(H-1, C-13 and P-31) spectroscopy and single-crystal X-ray diffraction. The structures show L to be positioned on opposite sides of the metal with the nitrates forming an equatorial band. When Ln = Dy, Er, and Lu two distinct molecules are present in the unit cell. A major isomer (70%) has a (P)O-Ln-O(P) angle of less than 180 degrees with one of the nitrate ligands twisted out of the plane of the other nitrates while the lower abundance isomer is more symmetric with the (P)O-Ln-O(P) angle of 180 degrees and the nitrate ligands coplanar giving a hexagonal bipyramidal geometry. These isomers cannot be observed by variable temperature solution P-31 NMR measurements but are clearly seen in the solid-state NMR spectrum of the Lu complex. Variable temperature solid-state NMR indicates that the isomers do not interconvert at temperatures up to 100 degrees C. Attempts to prepare cationic species [Ln(NO3)(2)L-3](+)[PF6](-) have not been totally successful and led to the isolation of crystals of Lu(NO3)(3)L-2 and Tb(NO3)(3)L-2 center dot CH3CN (8).
0020-1669
4379-4389
Bowden, Allen
56c1b364-6752-494e-97fa-ea2d8b161124
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Platt, Andrew W. G.
1d1677ab-01a7-4a16-905b-4ce7a28f73d1
Bowden, Allen
56c1b364-6752-494e-97fa-ea2d8b161124
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Platt, Andrew W. G.
1d1677ab-01a7-4a16-905b-4ce7a28f73d1

Bowden, Allen, Coles, Simon J., Pitak, Mateusz B. and Platt, Andrew W. G. (2012) Complexes of lanthanide nitrates with tri tert butylphosphine oxide. Inorganic Chemistry, 51 (7), 4379-4389. (doi:10.1021/ic300142r).

Record type: Article

Abstract

Reaction of lanthanide nitrates with (Bu3PO)-Bu-t (=L) lead to the isolation of complexes Ln(NO3)(3)L-2 center dot H2O center dot nEtOH (Ln = La (1), Nd(2)), Ln(NO3)(3)L-2 center dot nEtOH (Sm(3), Eu(4)), and Ln(NO3)(3)L-2 (Dy(5), Er(6), Lu(7)). These have been characterized by elemental analysis, infrared and NMR(H-1, C-13 and P-31) spectroscopy and single-crystal X-ray diffraction. The structures show L to be positioned on opposite sides of the metal with the nitrates forming an equatorial band. When Ln = Dy, Er, and Lu two distinct molecules are present in the unit cell. A major isomer (70%) has a (P)O-Ln-O(P) angle of less than 180 degrees with one of the nitrate ligands twisted out of the plane of the other nitrates while the lower abundance isomer is more symmetric with the (P)O-Ln-O(P) angle of 180 degrees and the nitrate ligands coplanar giving a hexagonal bipyramidal geometry. These isomers cannot be observed by variable temperature solution P-31 NMR measurements but are clearly seen in the solid-state NMR spectrum of the Lu complex. Variable temperature solid-state NMR indicates that the isomers do not interconvert at temperatures up to 100 degrees C. Attempts to prepare cationic species [Ln(NO3)(2)L-3](+)[PF6](-) have not been totally successful and led to the isolation of crystals of Lu(NO3)(3)L-2 and Tb(NO3)(3)L-2 center dot CH3CN (8).

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More information

e-pub ahead of print date: 13 March 2012
Published date: 2 April 2012
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 345987
URI: https://eprints.soton.ac.uk/id/eprint/345987
ISSN: 0020-1669
PURE UUID: f2929aa5-8e74-4f1b-92fd-a8fbc7499fdf
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

Catalogue record

Date deposited: 10 Dec 2012 16:26
Last modified: 24 Sep 2019 00:52

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