Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide

Glazier, Mikael J; Levason, William; Matthews, Melissa L.; Thornton, Pamela L.; Webster, Michael

doi:10.1016/j.ica.2003.09.015

Cited by 38 publications

(35 citation statements)

References 16 publications

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“…Unfortunately, any t, including the two-, three-and four-legged scattering paths resulted in bad ts of this peak which might be due to highly distorted paths lengths. 47,48 The best t was obtained by including only the two-legged scattering path Ln-P. This resulted in a coordination number of 4.5(4), a DebyeWaller factor of 0.01(1)Å 2 and a path length of 3.788(7)Å.…”

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Separation of rare-earth ions from ethylene glycol (+LiCl) solutions by non-aqueous solvent extraction with Cyanex 923

et al. 2017

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The separation of a mixture of rare earths by non-aqueous solvent extraction with two immiscible organic phases has been studied. The more polar organic phase was ethylene glycol with dissolved lithium chloride and the less polar organic phase was the extractant diluted in n-dodecane. Cyanex 923 was found to be the most performant extractant amongst the investigated acidic, basic and solvating extractants: Cyanex 272, Cyphos IL 101, Aliquat 336, bis(2-ethylhexyl)amine, trioctylphosphine oxide (TOPO) and Cyanex 923. The replacement of the aqueous chloride feed solutions by non-aqueous ethylene glycol feed solutions had a profound effect on the distribution ratios and separation factors. The separation factors for extraction of pairs of rare earths from aqueous chloride solutions by Cyanex 923 are too low to be of practical use.On the contrary, a mixture of rare earths can be separated conveniently in four different groups by extraction with Cyanex 923 from ethylene glycol (+LiCl) solutions. The influence of several parameters such as the chloride concentration, the type of chloride salt, the addition of other polar solvents to the ethylene glycol phase, the addition of second extractant to the less polar organic phase, and the addition of complexing agents to the ethylene glycol phase has been studied. The extraction mechanism for extraction of ytterbium(III) was studied by slope analysis experiments. The ytterbium(III) species in the ethylene glycol phase and the extracted species in the n-dodecane phase were determined by EXAFS.Furthermore, a conceptual flow sheet for the fractionation of rare earths from an ethylene glycol (+LiCl) feed solution into different groups by extraction with Cyanex 923 has been proposed. The new extraction system is useful for extraction of scandium and for separation of scandium from the other REEs.

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“…Mark that this rather long path length is due to the almost linear Ln-O-P bond angle, which is also found in different crystal structures of lanthanides with phosphine oxides. 46,48 Moreover, exact bond length is probably lower, as the peak is tted at slightly higher distance.…”

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Separation of rare-earth ions from ethylene glycol (+LiCl) solutions by non-aqueous solvent extraction with Cyanex 923

et al. 2017

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“…Anhydrous complexes are frequently formed in reactions from which water is not rigorously excluded. Thus triaryl and smaller trialkyl phosphine oxides (R 3 PO) form complexes based on [LnX 3 (R 3 PO) 3 ] or [LnX 2 (R 3 PO) 4 ] + when X = Cl, Br, and OTf, with the phosphine oxide directly bonded to the metal. The formation of hydrated complexes here would seem to be driven by the steric and electronic demands of the ligands.…”

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Synthesis, Structural Characterisation and Solution Behaviour of High‐Symmetry Lanthanide Triflate Complexes with the Sterically Demanding Phosphine Oxides Cy₃PO and tBu₃PO

2017

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The synthesis and characterisation of complexes formed from lanthanide trifluoromethanesulfonates [Ln(OTf)3] and tricyclohexylphosphine oxide (Cy3PO) or tri‐tert‐butylphosphine oxide (tBu3PO) are described. The structures of [Ln(H2O)5(Cy3PO)2]·2R3PO·(OTf)3 (Ln = Pr, Tm; R = Cy and Ln = Nd; R = tBu) are pentagonal bipyramidal with an equatorial plane of five H2O ligands and two axial Cy3PO ligands. The remaining Cy3PO molecules are H‐bonded to the coordinated water molecules, as are the triflate anions. NMR spectroscopy showed that the triflate ions remain associated with the complexes in CDCl3 solution. Lanthanide‐induced shifts in the 19F and 31P NMR spectra confirm that one structure is present for all the lanthanides with an additional structure for the heavier metals. The acidity of the complexes was examined by 31P NMR spectroscopic studies on the reactions between [Ln(H2O)5(Cy3PO)2]·2Cy3PO·(OTf)3 (Ln = La, Eu, Er, Lu) and phosphines PR3 (R = Ph, mesityl, Cy), Ph2PC2H4PPh2 and Ph2PC3H6PPh2. Protonation of the more basic phosphines and H‐bonding to the less basic phosphines is observed.

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“…A broad 31 P{ 1 H } -NMR signal at approximately 40 ppm is typical for metal-coordinated phosphine oxides (Mecking and Keim, 1996;Levason et al, 2000;Saravanabharathi et al, 2002;Glazier et al, 2004;Farrer et al, 2010).…”

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Synthesis and molecular structure of the novel bismuth(III) sulfonate complex [Bi(C18H14P(O)SO3)2(DMSO)3](NO3)∙DMSO∙2H2O

Schlesinger¹,

Rüffer²,

Lang³

et al. 2012

Main Group Metal Chemistry

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The synthesis of [Bi(C 18 H 14 P(O)SO 3 ) 2 (DMSO) 3 ] (NO 3 )‧DMSO‧2H 2 O starting from [Bi 6 O 4 (OH) 4 ](NO 3 ) 6 ‧H 2 O and 2-(diphenylphosphino)benzenesulfonic acid is presented. 31 P{ 1 H } -NMR experiments confirm the in situ oxidation of 2-(diphenylphosphino)benzenesulfonic acid to give 2-(diphenylphosphine oxide)benzenesulfonic acid by heating in dimethyl sulfoxide (DMSO). In the presence of [Bi 6 O 4 (OH) 4 ](NO 3 ) 6 ‧H 2 O, subsequent formation of single crystals of the title compound is observed. The crystal structure determination reveals that the bismuth atom shows a [5 + 4] coordination with short BiϪO distances in the range of 2.278(11) to 2.398(11) Å to the oxygen atoms of DMSO and phosphine oxide groups and with longer BiϪO bonds of 2.74(2) and 2.88(2) Å to the chelating sulfonate groups.

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Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide

Cited by 38 publications

References 16 publications

Separation of rare-earth ions from ethylene glycol (+LiCl) solutions by non-aqueous solvent extraction with Cyanex 923

Separation of rare-earth ions from ethylene glycol (+LiCl) solutions by non-aqueous solvent extraction with Cyanex 923

Synthesis, Structural Characterisation and Solution Behaviour of High‐Symmetry Lanthanide Triflate Complexes with the Sterically Demanding Phosphine Oxides Cy₃PO and tBu₃PO

Synthesis and molecular structure of the novel bismuth(III) sulfonate complex [Bi(C18H14P(O)SO3)2(DMSO)3](NO3)∙DMSO∙2H2O

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Synthesis, properties and solution speciation of lanthanide chloride complexes of triphenylphosphine oxide

Cited by 38 publications

References 16 publications

Separation of rare-earth ions from ethylene glycol (+LiCl) solutions by non-aqueous solvent extraction with Cyanex 923

Separation of rare-earth ions from ethylene glycol (+LiCl) solutions by non-aqueous solvent extraction with Cyanex 923

Synthesis, Structural Characterisation and Solution Behaviour of High‐Symmetry Lanthanide Triflate Complexes with the Sterically Demanding Phosphine Oxides Cy3PO and tBu3PO

Synthesis and molecular structure of the novel bismuth(III) sulfonate complex [Bi(C18H14P(O)SO3)2(DMSO)3](NO3)∙DMSO∙2H2O

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Synthesis, Structural Characterisation and Solution Behaviour of High‐Symmetry Lanthanide Triflate Complexes with the Sterically Demanding Phosphine Oxides Cy₃PO and tBu₃PO