Synthesis and structure of [CeF4(Me2SO)2]—A rare neutral ligand complex of a lanthanide tetrafluoride

Champion, Martin J. D.; Levason, William; Reid, Gillian

doi:10.1016/j.jfluchem.2013.10.014

Cited by 11 publications

(3 citation statements)

References 9 publications

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“…They too are likely to contain only lattice/surface water. 32 The wider implications of these results in metal fluoride coordination chemistry suggest that for other metals, only those 'hydrated' fluorides that contain water within the metal coordination sphere, are likely to be viable synthons for neutral ligand complexes.…”

Section: Attempted Synthesis From Mfmentioning

confidence: 99%

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

et al. 2018

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Fluorination of [ScCl3(Me3-tacn)] (Me3-tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) and [ScCl3(BnMe2-tacn)] (BnMe2-tacn = 1,4-dimethyl-7-benzyl-1,4,7-triazacyclononane) by Cl/F exchange with 3 mol. equiv. of anhydrous [NMe4]F in CH3CN solution yields the corresponding [ScF3(R3-tacn)] (R3 = Me3 or BnMe2). These are the first examples of scandium fluoride complexes containing neutral co-ligands. The fluorination occurs stepwise, and using a deficit of [NMe4]F produced [ScF2Cl(Me3-tacn)]. Attempts to fluorinate [YCl3(Me3-tacn)], [YI3(Me3-tacn)], [LaCl3(Me3-tacn)(OH2)] or [MCl3(terpy)] (M = Sc, Y or La; terpy = 2,2':6'2''-terpyridyl) using a similar method were unsuccessful, due to the Cl/F exchange being accompanied by loss of the neutral ligand from the metal centre. Fluorination of [ScCl3(Me3-tacn)] or [ScCl3(terpy)] with Me3SnF was also successful. The products were identified as the very unusual heterobimetallic [Sc(Me3-tacn)F2(μ-F)SnMe3Cl] and [Sc(terpy)F(μ-F)2(SnMe3Cl)2], in which the Me3SnCl formed in the reaction behaves as a weak Lewis acid towards the scandium fluoride complex, linked by Sc-F-Sn bridges. [Sc(terpy)F(μ-F)2(SnMe3Cl)2] decomposes irreversibly in solution but, whilst multinuclear NMR data show that [Sc(Me3-tacn)F2(μ-F)SnMe3Cl] is dissociated into the [ScF3(Me3-tacn)] and Me3SnCl in CH3CN solution, the bimetallic complex reforms upon evaporation of the solvent. The new scandium fluoride complexes and the chloride precursors have been characterised by microanalysis, IR and multinuclear NMR (1H, 19F, 45Sc) spectroscopy as appropriate. X-ray crystal structures provide unambiguous evidence for the identities of [Sc(Me3-tacn)F2(μ-F)SnMe3Cl], [ScF2Cl(Me3-tacn)], [YI3(Me3-tacn)], [{YI2(Me3-tacn)}2(μ-O)], [ScCl3(terpy)], [YCl3(terpy)(OH2)], and [{La(terpy)(OH2)Cl2}2(μ-Cl)2]. Once formed, the [ScF3(R3-tacn)] complexes are stable in water and unaffected by a ten-fold excess of Cl- or MeCO2-, although they are immediately decomposed by excess F-. The potential use of [ScF3(R3-tacn)] type complexes as platforms for 18F PET (positron emission tomography) radiopharmaceuticals is briefly discussed. Attempts to use the Group 3 fluoride "hydrates", MF3·xH2O, as precursors were unsuccessful; no reaction with R3-tacn or terpy occurred either on reflux in CH3CN or under hydrothermal conditions (H2O, 180° C, 15 h). PXRD data showed that these "hydrates" actually contain the anhydrous metal trifluorides with small amounts of surface or interstitial water.

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Section: Attempted Synthesis From Mfmentioning

confidence: 99%

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

et al. 2018

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“…Probably as a result of the high lattice energies of lanthanide fluorides, there are no reports of phosphine oxide complexes with LnF 3 and attempts to prepare CeF 4 complexes using [CeF 4 (DMSO) 2 ] as a precursor were unsuccessful [43]. [47].…”

Section: Complexes With Lanthanide Halidesmentioning

confidence: 99%

“…9, have been determined and show the europium to be square antiprismatic in [Eu(CF 3 COCDCOCF 3 ) 3 (19) The photophysical properties of the complexes showed that [Eu (CF 3 COCDCOCF 3 ) 3 (41) 2 ] has a very sharp red emission with a wide stimulated emission cross-section. Complexes of (26), (43) and 44 antiprismatic about the europium ion [109,110]. The complex of (44) in particular, has a high emission quantum yield of 83%.…”

Section: Complexes With Lanthanide B-diketonatesmentioning

confidence: 99%

Lanthanide phosphine oxide complexes

Platt

2017

Coordination Chemistry Reviews

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Phosphine oxide complexes of lanthanide metal have been studied to elucidate the fundamental aspects of their structural chemistry and to develop important technological applications mainly in the reprocessing of nuclear fuels and in photoluminescent devices but also in other fields such as gas sorption and homogeneous catalysis. The aim of this review is to give an overview of the range of complexes with phosphine oxides and trivalent lanthanide and yttrium ions, their structural features and applications.

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The Rare Earths, a Challenge to Mendeleev, No Less Today

Cotton

2021

Perspectives on the History of Chemistry

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Synthesis and structure of [CeF4(Me2SO)2]—A rare neutral ligand complex of a lanthanide tetrafluoride

Cited by 11 publications

References 9 publications

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

Group 3 metal trihalide complexes with neutral N-donor ligands – exploring their affinity towards fluoride

Lanthanide phosphine oxide complexes

The Rare Earths, a Challenge to Mendeleev, No Less Today

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