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Cerium(III) and cerium(IV) nitrate complexes of trialkylphosphine oxides

Cerium(III) and cerium(IV) nitrate complexes of trialkylphosphine oxides
Cerium(III) and cerium(IV) nitrate complexes of trialkylphosphine oxides
The reactions of ammonium cerium(IV) nitrate, (NH4)2Ce(NO3)6 (CAN) with trialkylphosphine oxides, R3PO (R = Et, iPropyl, nBu3, iBu3PO, tBu3PO, Cy3PO (Cy = cyclohexyl) and Oct3PO (Oct = n-octyl)) have been investigated by 31-P NMR spectroscopy in a variety of conditions. Reactions with acetone solutions of excess of CAN and R3PO and of solid CAN with chloroform solutions of R3PO and aqueous solutions of CAN with chloroform solutions of R3PO led to the observation of Ce(NO3)4(R3PO)2. 31-P NMR spectroscopy and conductimetric titration of acetone solutions of CAN with R3PO confirm the initial reactions is the formation of Ce(NO3)4(R3PO)2 (R = Et, Bu, Cy, Oct) followed by a slower reaction to form the ionic [Ce(NO3)3(R3PO)3][NO3]. The isolation of pure complexes has not proved possible in most cases but crystals suitable for x-ray analysis were extracted in some instances. The structures of the Ce(IV) complexes [Ce(NO3)4(Cy3PO)2] and [Ce(NO3)3(Et3PO)3][NO3] and the related Ce(III) complexes [Ce(NO3)3(Cy3PO)3] and [Ce(NO3)3(H2O)3(Et3PO)] are reported.
cerium(IV) nitrate, phosphine oxide, Structure
0277-5387
346-351
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Fieldhouse, Sarah J.
c03807d2-a231-4f5d-8ad4-157e1b1b4689
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Platt, Andrew W.G.
2148bd66-0f68-4390-a262-e57ac72f52f2
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Fieldhouse, Sarah J.
c03807d2-a231-4f5d-8ad4-157e1b1b4689
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Platt, Andrew W.G.
2148bd66-0f68-4390-a262-e57ac72f52f2

Coles, Simon J., Fieldhouse, Sarah J., Klooster, Wim and Platt, Andrew W.G. (2019) Cerium(III) and cerium(IV) nitrate complexes of trialkylphosphine oxides. Polyhedron, 161, 346-351. (doi:10.1016/j.poly.2019.01.031).

Record type: Article

Abstract

The reactions of ammonium cerium(IV) nitrate, (NH4)2Ce(NO3)6 (CAN) with trialkylphosphine oxides, R3PO (R = Et, iPropyl, nBu3, iBu3PO, tBu3PO, Cy3PO (Cy = cyclohexyl) and Oct3PO (Oct = n-octyl)) have been investigated by 31-P NMR spectroscopy in a variety of conditions. Reactions with acetone solutions of excess of CAN and R3PO and of solid CAN with chloroform solutions of R3PO and aqueous solutions of CAN with chloroform solutions of R3PO led to the observation of Ce(NO3)4(R3PO)2. 31-P NMR spectroscopy and conductimetric titration of acetone solutions of CAN with R3PO confirm the initial reactions is the formation of Ce(NO3)4(R3PO)2 (R = Et, Bu, Cy, Oct) followed by a slower reaction to form the ionic [Ce(NO3)3(R3PO)3][NO3]. The isolation of pure complexes has not proved possible in most cases but crystals suitable for x-ray analysis were extracted in some instances. The structures of the Ce(IV) complexes [Ce(NO3)4(Cy3PO)2] and [Ce(NO3)3(Et3PO)3][NO3] and the related Ce(III) complexes [Ce(NO3)3(Cy3PO)3] and [Ce(NO3)3(H2O)3(Et3PO)] are reported.

Text
Polyhedron 2019 - Accepted Manuscript
Restricted to Repository staff only until 24 January 2020.
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More information

Accepted/In Press date: 12 January 2019
e-pub ahead of print date: 24 January 2019
Published date: 15 March 2019
Keywords: cerium(IV) nitrate, phosphine oxide, Structure

Identifiers

Local EPrints ID: 428243
URI: https://eprints.soton.ac.uk/id/eprint/428243
ISSN: 0277-5387
PURE UUID: 8cd265fc-686b-4d27-94ec-94f7154d6360
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 18 Feb 2019 17:30
Last modified: 13 Apr 2019 00:36

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