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Cerium(IV) nitrate complexes with bidentate phosphine oxides

Cerium(IV) nitrate complexes with bidentate phosphine oxides
Cerium(IV) nitrate complexes with bidentate phosphine oxides

The reactions between ceric ammonium nitrate, (NH4)2Ce(NO3)6, (CAN) and the bidentate phosphine oxides, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene (L1), oxydi-2,1-phenylene bis(diphenylphosphine dioxide) (L2), 1,2-bis(diphenylphosphino)ethane dioxide (L3) and 1,4-bis(diphenylphosphino)butane dioxide, L4 have been investigated. The crystal structures of the molecular Ce(NO3)4L1 (1), and ionic [Ce(NO3)3L32][NO3]⋅CHCl3 (3), [Ce(NO3)3L32][NO3] (4) and the polymeric [Ce(NO3)3L41.5] [NO3] (5) and the cerium(III) complex [Ce(NO3)2L12][NO3] (2) are reported. The thermal stability of the complexes has been examined by thermogravimetry with the gaseous decomposition products analysed by infrared spectroscopy. Evolution of CO2 is found for both Ce(III) and Ce(IV) complexes with the later also forming NO2. The formation of the complexes in solution has been studied by 31P NMR spectroscopy and further complexes [Ce(NO3)3L12]+[NO3]− and [Ce(NO3)2L13]2+2[NO3]− identified in CD3CN solution. The complex (1) exists as a single molecular species in solution and is stable in dichloromethane whilst (3) decomposes on standing in both CD2Cl2 and CD3CN to Ce(III) containing species. Complexes of L2 have been identified by solution 31P NMR spectroscopy and these decompose in solution to give Ce(NO3)3L22. This study represents the first structural characterisations of Ce(IV) complexes with bidentate phosphine oxides.

Cerium, coordination complexes, NMR spectroscopy, thermogravimetry, X-ray diffraction
1434-1948
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Cooper, Simon
ae5da05c-44a3-47aa-874b-77e3ff160c80
Klooster, Wim T.
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McCormick Mc Pherson, Laura J.
987149b5-9dc8-4e52-80a7-5bd268402e7e
Platt, Andrew W.G.
1d1677ab-01a7-4a16-905b-4ce7a28f73d1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Cooper, Simon
ae5da05c-44a3-47aa-874b-77e3ff160c80
Klooster, Wim T.
64dc0111-f415-4226-9189-45764c0933d9
McCormick Mc Pherson, Laura J.
987149b5-9dc8-4e52-80a7-5bd268402e7e
Platt, Andrew W.G.
1d1677ab-01a7-4a16-905b-4ce7a28f73d1

Coles, Simon J., Cooper, Simon, Klooster, Wim T., McCormick Mc Pherson, Laura J. and Platt, Andrew W.G. (2023) Cerium(IV) nitrate complexes with bidentate phosphine oxides. European Journal of Inorganic Chemistry, 26 (32), [e202300375]. (doi:10.1002/ejic.202300375).

Record type: Article

Abstract

The reactions between ceric ammonium nitrate, (NH4)2Ce(NO3)6, (CAN) and the bidentate phosphine oxides, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene (L1), oxydi-2,1-phenylene bis(diphenylphosphine dioxide) (L2), 1,2-bis(diphenylphosphino)ethane dioxide (L3) and 1,4-bis(diphenylphosphino)butane dioxide, L4 have been investigated. The crystal structures of the molecular Ce(NO3)4L1 (1), and ionic [Ce(NO3)3L32][NO3]⋅CHCl3 (3), [Ce(NO3)3L32][NO3] (4) and the polymeric [Ce(NO3)3L41.5] [NO3] (5) and the cerium(III) complex [Ce(NO3)2L12][NO3] (2) are reported. The thermal stability of the complexes has been examined by thermogravimetry with the gaseous decomposition products analysed by infrared spectroscopy. Evolution of CO2 is found for both Ce(III) and Ce(IV) complexes with the later also forming NO2. The formation of the complexes in solution has been studied by 31P NMR spectroscopy and further complexes [Ce(NO3)3L12]+[NO3]− and [Ce(NO3)2L13]2+2[NO3]− identified in CD3CN solution. The complex (1) exists as a single molecular species in solution and is stable in dichloromethane whilst (3) decomposes on standing in both CD2Cl2 and CD3CN to Ce(III) containing species. Complexes of L2 have been identified by solution 31P NMR spectroscopy and these decompose in solution to give Ce(NO3)3L22. This study represents the first structural characterisations of Ce(IV) complexes with bidentate phosphine oxides.

Text
Eur J Inorg Chem - 2023 - Coles - Cerium IV Nitrate Complexes With Bidentate Phosphine Oxides - Version of Record
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e-pub ahead of print date: 24 July 2023
Published date: 14 November 2023
Additional Information: Funding Information: We are grateful to the EPSRC for the use of the National Crystallography Service at Southampton University.[42] Publisher Copyright: © 2023 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.
Keywords: Cerium, coordination complexes, NMR spectroscopy, thermogravimetry, X-ray diffraction

Identifiers

Local EPrints ID: 483752
URI: http://eprints.soton.ac.uk/id/eprint/483752
DOI: doi:10.1002/ejic.202300375
ISSN: 1434-1948
PURE UUID: e4df1820-2381-4968-82c3-a8603891fbc3
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 03 Nov 2023 18:11
Last modified: 18 Mar 2024 02:50

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Contributors

Author: Simon J. Coles ORCID iD
Author: Simon Cooper
Author: Wim T. Klooster
Author: Laura J. McCormick Mc Pherson
Author: Andrew W.G. Platt

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