cas 54761-04-5, YTTERBIUM(III) TRIFLUOROMETHANESULFONATE HYDRATE

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Structural and electrochemical properties of YbIII in various ionic liquids
Solvation and ligand exchange reactions of ytterbium(III) as a model for the late trivalent f-elements have been studied in triflate and bistriflylamide ionic liquids (ILs) with the purpose of contributing to a wider understanding of f-element organometallic catalysis, as well as separation and nuclear fuel reprocessing, in ILs. Using the compounds [C4mpyr] 3[Yb(OTf)6] and [C4mpyr][Yb(Tf 2N)4] [C4mpyr = N-methyl-N-propylpyrrolidinium; OTf = triflate, trifluoromethanesulfonate; Tf2N = bistriflylamide, bis(trifluoromethanesulfonyl)amide] we were able to structurally characterize the local surroundings of Yb3+ in the ILs [C4mpyr][OTf] and [C4mpyr][Tf2N]unequivocally. The formation of [C 4mpyr]3[Yb(OTf)6][C4mpyr][Tf 2N] from a solution of Yb(Tf2N)3 in [C 4mpyr][OTf] shows that the stronger coordinating OTf- anion completely replaces the less Lewis basic Tf2N- anion in the first coordination sphere of the lanthanide ion. As expected, such a ligand exchange could not be observed for Yb(OTf)3 in [C 4mpyr][Tf2N]. The ion exchange in the lanthanide coordination sphere can be efficiently monitored by means of cyclic voltammetry (CV). CV measurements also indicate that Yb3+ adopts a mixed OTf -/Tf2N- coordination environment when Yb(OTf)3 is dissolved in [C4mpyr][Tf2N]. The measured half-wave potentials of the studied systems can be linked to the electron-donor properties of the metal cation. Solvation and ligand exchange reactions of ytterbium(III) as a model for the later trivalent lanthanides have been studied in triflate and bistriflylamide ionic liquids (ILs) with the purpose of contributing to a wider understanding of organometalliccatalysis, as well as separation and nuclear fuel reprocessing, in ILs.
Babai, Arash,Pitula, Slawomir,Mudring, Anja-Verena
p. 4933 - 4937
(2010)
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Change in spin state and enhancement of redox reactivity of photoexcited states of aromatic carbonyl compounds by complexation with metal ion salts acting as Lewis acids. Lewis acid-catalyzed photoaddition of benzyltrimethylsilane and tetramethyltin via p
The lowest excited state of aromatic carbonyl compounds (naphthaldehydes, acetonaphthones, and 10-methylacridone) is changed from the n,π* triplet to the π,π* singlet which becomes lower in energy than the n,π* triplet by the complexation with metal ions
Fukuzumi,Satoh,Okamoto,Yasui,Suenobu,Seko,Fujitsuka,Ito
p. 7756 - 7766
(2001)
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Electrodeposition of rare earth metals Y, Gd, Yb in ionic liquids
The possibility of yttrium, gadolinium, and ytterbium electrodeposition from solutions of their triflates in different ionic liquids at 100°C was investigated. It was shown that these metals could be deposited on the cathode from electrolytes based on ionic liquids with quaternary ammonium cations, and these metals do not deposit from 1-butyl-2,3-dimethylimidazolium triflate. It was established that, in the case of butyltrimethylamonium triflate usage, metal deposition occurs on a copper electrode, and it does not occur on a platinum electrode, and in 1-butyl-1-methylpirrolidinium triflate, the reduction process is possible on both electrodes. Yb3+ reduction occurs step by step via Yb2+ formation. It was shown that the limiting stage of the cathode process is adsorption of a metal cation on the electrode.
Glukhov,Greish,Kustov
p. 104 - 108
(2010)
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Effective and recoverable homogeneous catalysts for the transesterification of dimethyl carbonate with ethanol: Lanthanide triflates
The catalytic activities of metal triflates were tested for the transesterification of dimethyl carbonate (DMC) with ethanol. It was found that yttrium triflate was the most efficient homogeneous catalyst. When the transesterification reaction was catalyz
Mei,Chen,Li
p. 666 - 670
(2009)
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TG-DTA study on the lanthanoid trifluoromethanesulfonate complexes
The thermal decomposition of the lanthanoid trifluoromethanesulfonate (triflate) complexes {Ln(CF3SO3)3·9H2O; Ln=La-Lu} was studied by TG and DTA methods. From the endothermic and exothermic data of Ln(CF3SO3)3·9H2O complexes, pyrolysis behavior of the complexes is classified into three groups: 1) La-Nd salts, 2) Sm-Ho salts, 3) Er-Lu salts. It has also shown that all the final decomposition products were found to result in the formation of LnF3.
Egashira,Yoshimura,Kanno,Suzuki
p. 501 - 508
(2008/10/08)

Metal ion-catalyzed Diels-Alder and hydride transfer reactions. Catalysis of metal ions in the electron-transfer step
Rates of Diels - Alder cycloaddition of anthracenes with p-benzoquinone and its derivatives as well as rates of hydride-transfer reactions from 10-methyl-9,10-dihydroacridine to the same series of p-benzoquinones are accelerated significantly in the presence of metal ions in acetonitrile. An extensive comparison of the catalytic effects of metal ions in electron transfer from one-electron reductants (cobalt tetraphenylporphyrin and decamethyrferrocene) to p-benzoquinones with those in the Diels - Alder reactions of the quinones as well as the hydride-transfer reactions has revealed that the catalysis of metal ions in each case is ascribed to the 1:1 and 1:2 complexes formed between the corresponding semiquinone radical anions and metal ions. The transient absorption and ESR spectra of the semiquinone radical anion-metal ion complexes are detected directly in the electron-transfer reduction of p-benzoquinone derivatives in the presence of metal ions. The catalytic reactivities of a variety of metal ions in each reaction are well correlated with the energy splitting values of πg levels because of the complex formation between O2.- andMn+, which are derived from the gzz values of the ESR spectra of the O2.--Mn+ complex.
Fukuzumi, Shunichi,Ohkubo, Kei,Okamoto, Toshihiko
p. 14147 - 14155
(2007/10/03)

Synthese und Strukturen von Bis(triethanolamin)lanthanoid-Komplexen
Synthesis and Structures of Bis(triethanolamine)lanthanide Complexes Three novel lanthanide triethanolamine chelates (CF3SO3)3 (Ln = Pr, 1; Yb, 2; Lu, 3) were synthesized from Ln(CF3SO3)3 and triethanolamine in THF.The structures of 1 and 2 were determined by single-crystal X-ray diffraction studies.The isostructural compounds crystallize with three molecules of THF and possess nonacoordinate lanthanide ions with a monocapped tetragonal antiprismatic coordination geometry.
Hahn, Ekkehardt F.,Mohr, Joerg
p. 481 - 484
(2007/10/02)

Characterization of a series of lanthanide amine cage complexes
The preparation and characterization of a series of encapsulated lanthanide amine complexes are discussed. The complexes of Ce, Pr, Eu, and Y with the ligand 1,9-bis(2-aminoethyl)-1,4,6,9,12,14-hexaazacyclohexadecane (referred to as L) have been prepared by using the previously described template approach (using La and Yb) involving the combination of the metal trifluoromethanesulfonate (triflate or trif) salt as the template source, 2 equiv of the tetradentate amine 2,2′,2″-tris(2-aminoethyl)amine (tren), and an excess of the formaldehyde derivative bis(dimethylamino)methane. The reduction potentials of the europium and ytterbium complexes are -0.68 and -1.37 V (vs SCE, in propylene carbonate), respectively, suggesting that this ligand imparts a large stabilization of the +3 oxidation state relative to the +2 state. An analogous lanthanum triflate complex, La(L′)(trif)3 [L′ = bis((2-(bis(2-aminoethyl)amino)ethyl)amino)methane], with one methylene bridge has been prepared and characterized by single-crystal X-ray crystallography. The structure is similar to that of the previously described dibridged complex La(L)(trif)3·CH3CN, and a comparison of these structures suggests possible explanations for the difficulties of obtaining the fully encapsulated lanthanide complex. The complex crystallizes in space group P1 with Z = 2 and a = 9.8448 (13) A?, b = 11.0620 (15) A?, c = 16.8557 (19) A?, α = 73.456 (9)°, β = 73.684 (10)°, and γ = 70.548 (11)°. For 6065 independent data with Fo2 > 3σ(Fo2), full-matrix least-squares refinement with anisotropic thermal parameters for all non-hydrogen atoms (except disordered atoms) converged to unweighted and weighted R factors of 2.4 and 3.0%, respectively. The conductivities of acetonitrile solutions of these complexes suggest 1:1 and 1:2 electrolytes at millimolar concentrations but are highly concentration dependent, indicating that acetonitrile competes effectively with the triflate anions for the free coordination sites on the metal ion. A similar reaction produces in small yield what we believe to be a fully encapsulated ytterbium ion, Yb(L″)(trif)3·CH3CN [L″ = 1,4,6,9,12,14,19,21-octaazabicyclo[7.7.7]tricosane]. In contrast to the di- and monobridged complexes, this new complex does not develop a precipitate in the presence of water, which suggests that the fully encapsulated species is stable toward hydrolysis. The preparation and molecular structure of the first example of a mixed-ligand lanthanide amine complex, Pr(tren)(trien)(trif)3 (trien = triethylenetetramine), is presented in an attempt to characterize the preferred geometry and appropriate bridging units for interconnecting the amine groups. The metal ion is nine-coordinate with tetradentate tren and trien ligands and one coordinated triflate anion. This complex also crystallizes in space group P1 with Z = 2 and a = 9.5259 (12) A?, b = 10.6600 (14) A?, c = 17.0802 (25) A?, α = 74.284 (12)°, β = 76.914 (11)°, and γ = 85.500 (10)°. For 2738 independent data with Fo2 > 3σ(Fo2), a similar refinement converged to unweighted and weighted R factors of 3.9 and 4.6%, respectively.
Smith, Paul H.,Reyes, Zelideth E.,Lee, Chi-Woo,Raymond, Kenneth N.
p. 4154 - 4165
(2008/10/08)