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Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides

Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides
Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides
The reaction of OPR3 (R = Me, Ph) with YbI2, EuI2 and EuBr2 in rigorously anhydrous MeCN under N2 produces the divalent lanthanide complexes [LnX2(OPR3)4] (Ln = Yb, Eu, X = I; Ln = Eu X= Br) in moderate to good yield, whilst [SmI2(OPR3)4] were obtained from SmI2 and OPR3 in dry, degassed thf. These are the first examples involving divalent lanthanide ions and the complexes have been characterised by microanalysis, IR, UV/visible and 31P{1H} NMR spectroscopy. The X-ray crystal structure of [EuI2(OPPh3)4]⋅MeCN confirmed the six-coordinate Eu(II) species with a cis-octahedral geometry, which IR spectroscopy suggests is present in all of the OPPh3 complexes. In contrast the [LnX2(OPMe3)4] complexes appear to be trans isomers. The OPPh3 complexes are readily oxidised by dry O2 or I2, yielding the corresponding trivalent cations, [LnX2(OPPh3)4]+; a crystal structure of the product formed by oxidation of [EuI2(OPPh3)4] in MeCN solution confirms this to be [EuI2(OPPh3)4]I31.5MeCN, containing a trans-octahedral cation.
ytterbium diiodide, samarium diiodide, europium diiodide, europium dibromide, phosphine oxide, crystal structure
0277-5387
259-262
Bannister, Robert D.
4dd3eb2a-5ba7-46de-9277-8dd7e8e39b74
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bannister, Robert D.
4dd3eb2a-5ba7-46de-9277-8dd7e8e39b74
Levason, William
e7f6d7c7-643c-49f5-8b57-0ebbe1bb52cd
Light, Mark E.
cf57314e-6856-491b-a8d2-2dffc452e161
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037

Bannister, Robert D., Levason, William, Light, Mark E. and Reid, Gillian (2018) Tertiary phosphine oxide complexes of lanthanide diiodides and dibromides. Polyhedron, 154, 259-262. (doi:10.1016/j.poly.2018.07.057).

Record type: Article

Abstract

The reaction of OPR3 (R = Me, Ph) with YbI2, EuI2 and EuBr2 in rigorously anhydrous MeCN under N2 produces the divalent lanthanide complexes [LnX2(OPR3)4] (Ln = Yb, Eu, X = I; Ln = Eu X= Br) in moderate to good yield, whilst [SmI2(OPR3)4] were obtained from SmI2 and OPR3 in dry, degassed thf. These are the first examples involving divalent lanthanide ions and the complexes have been characterised by microanalysis, IR, UV/visible and 31P{1H} NMR spectroscopy. The X-ray crystal structure of [EuI2(OPPh3)4]⋅MeCN confirmed the six-coordinate Eu(II) species with a cis-octahedral geometry, which IR spectroscopy suggests is present in all of the OPPh3 complexes. In contrast the [LnX2(OPMe3)4] complexes appear to be trans isomers. The OPPh3 complexes are readily oxidised by dry O2 or I2, yielding the corresponding trivalent cations, [LnX2(OPPh3)4]+; a crystal structure of the product formed by oxidation of [EuI2(OPPh3)4] in MeCN solution confirms this to be [EuI2(OPPh3)4]I31.5MeCN, containing a trans-octahedral cation.

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Accepted/In Press date: 31 July 2018
e-pub ahead of print date: 9 September 2018
Published date: 1 November 2018
Keywords: ytterbium diiodide, samarium diiodide, europium diiodide, europium dibromide, phosphine oxide, crystal structure

Identifiers

Local EPrints ID: 423058
URI: http://eprints.soton.ac.uk/id/eprint/423058
ISSN: 0277-5387
PURE UUID: fad31539-7f83-4559-80a1-9b0f779ec370
ORCID for William Levason: ORCID iD orcid.org/0000-0003-3540-0971
ORCID for Mark E. Light: ORCID iD orcid.org/0000-0002-0585-0843
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

Catalogue record

Date deposited: 13 Aug 2018 16:30
Last modified: 17 Dec 2019 05:16

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