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]I31.5MeCN, containing a trans-octahedral cation.
ytterbium diiodide, samarium diiodide, europium diiodide, europium dibromide, phosphine oxide, crystal structure
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
1 November 2018
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, .
(doi:10.1016/j.poly.2018.07.057).
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]I31.5MeCN, containing a trans-octahedral cation.
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LnI2 29_07_2018 revised version (002)
- Accepted Manuscript
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1-s2.0-S027753871830456X-main
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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
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Date deposited: 13 Aug 2018 16:30
Last modified: 16 Mar 2024 06:59
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Author:
Robert D. Bannister
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