Isotropic nuclear magnetic resonance shifts in ion-paired systems. Penta- and hexanitratolanthanate(III) complexes

Walker, Ian M.; Weeden, David H.

doi:10.1021/ic50122a013

Cited by 33 publications

(15 citation statements)

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“…The formation of a 4: 3 complex implies the formation of LnXg-species and we can therefore expect that such complexes will form only if these species are stable enough. This is the case for Ln(N03);-, at least in the solid state and for the lighter lanthanoid ions [32], for LnCla- [45] and, to a lesser extent, for Ln(NCS);- [46]. We have isolated 4: 3 complexes of 2 with some chlorides (cJ Table 7) but we were unable to obtain such complexes with isothiocyanates, either by crystallization from a solution, or by thermal decomposition of the corresponding 1 : 1 complexes.…”

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confidence: 90%

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Complexes of Lanthanoid Nitrates with 15‐Crown‐5 and 18‐Crown‐6 Ethers

Bünzli

Wessner

1981

Helvetica Chimica Acta

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SummaryComplexes between the heavier lanthanoid nitrates Ln (NO,), and 15-crown-5 (1) and 18-crown-6 (2) ethers were isolated and characterized. Both 1 : 1 and 4: 3 complexes are formed with each Ln(II1) ion, except in the case of Gd and 2. The thermal transformation of the 1 : l complexes into the corresponding 4 : 3 complexes was studied by thermogravimetry and by DSC. X-ray and vibrational data provide information about the structure of these complexes. The interaction between Ln(II1) ions and ligands 1 and 2 in non-aqueous solutions is discussed on the basis of conductometric, fluorescence, UV./VIS. and 'H-NMR. data. Only 1 : 1 complexes of 2 formed in solution and their formation constants range from logKf=4.4 (Ln=La) to 2.4 (Ln=Yb); for Eu, Kf of the 15-crown-5 and 18-crown-6 ether complexes are of the same order of magnitude. For La, Pr, Nd, Eu, Yb, a variable temperature NMR. study gave some indications about the chemical exchanges in solution.The factors which determine the stoichiometry of the complexes are discussed.

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confidence: 90%

“…Walker & Weeden have already noticed the dissociation of hexanitrato species into pentanitrato species [32]. The electronic spectra of 0.02 M solutions of Pr (NO& containing increasing amounts of 2 (Fig.…”

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confidence: 90%

Complexes of Lanthanoid Nitrates with 15‐Crown‐5 and 18‐Crown‐6 Ethers

Bünzli

Wessner

1981

Helvetica Chimica Acta

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“…[8] The NÀO stretching modes n 4 , n 1 , and n 2 , along with the bending mode n 6 are confirmed in these samples, [18] with the corresponding peaks observed at about ñ = 1450-1470, 1320-1350, 1034-1040, and 815-820 cm À1 . No other NÀO stretching mode was found.…”

Section: Resultsmentioning

confidence: 57%

“…[14] Moreover, ILCs have wide potential applications in dye-sensitized solar cells and biology studies. [15] Herein, we report a kind of new water-free rare-earthmetal ionic liquids composed of 1-alkyl-3-methylimidazoli- 2,4,6,8,12,14,16,18). The water-free structure of 6 ] was confirmed by the single-crystal structure of compound 1.…”

Section: Mim] Xà3 [Lna C H T U N G T R E N N U N G (Ncs) X a C H T U mentioning

confidence: 92%

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Water‐Free Rare‐Earth‐Metal Ionic Liquids/Ionic Liquid Crystals Based on Hexanitratolanthanate(III) Anion

Tang

et al. 2013

Chemistry A European J

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The hexanitratolanthanate anion (La(NO(3))(6)(3-)) is an interesting symmetric anion suitable to construct the component of water-free rare-earth-metal ionic liquids. The syntheses and structural characterization of eleven lanthanum nitrate complexes, [C(n)mim](3)[La(NO(3))(6)] (n=1, 2, 4, 6, 8, 12, 14, 16, 18), including 1,3-dimethylimidazolium hexanitratolanthanate ([C(1)mim](3)[La(NO(3))(6)], 1), 1-ethyl-3-methylimidazolium hexanitratolanthanate ([C(2)mim](3)[La(NO(3))(6)], 2), 1-butyl-3-methylimidazolium hexanitratolanthanate ([C(4)mim](3)[La(NO(3))(6)], 3), 1-isobutyl-3-methylimidazolium hexanetratolanthanate ([isoC(4)mim](3)[La(NO(3))(6)], 4), 1-methyl-3-(3'-methylbutyl)imidazolium hexanitratolanthanate ([MC(4)mim](3)[La(NO(3))(6)], 5), 1-hexyl-3-methylimidazolium hexanitratolanthanate ([C(6)mim](3)[La(NO(3))(6)], 6), 1-methyl-3-octylimidazolium hexanitratolanthanate ([C(8)mim](3)[La(NO(3))(6)], 7), 1-dodecyl-3-methylimidazolium hexanitratolanthanate ([C(12)mim](3)[La(NO(3))(6)], 8), 1-methyl-3-tetradecylimidazolium hexanitratolanthanate ([C(14)mim](3)[La-(NO(3))(6)], 9), 1-hexadecyl-3-methylimid-azolium hexanitratolanthanum ([C(16)dmim](3)[La(NO(3))(6)], 10), and 1-methyl-3-octadecylimidazolium hexanitratolanthanate ([C(18)mim](3)[La(NO(3))(6)], 11) are reported. All new compounds were characterized by (1)H and (13)C NMR, and IR spectroscopy as well as elemental analysis. The crystal structure of compound 1 was determined by using single-crystal X-ray diffraction, giving the following crystallographic information: monoclinic; P2(1)/c; a=15.3170 (3), b=14.2340 (2), c=13.8954(2) Å; β=94.3453(15)°, V=3020.80(9) Å(3), Z=4, ρ=1.764 g cm(-3). The coordination polyhedron around the lanthanum ion is rationalized by six nitrate anions with twelve oxygen atoms. No hydrogen-bonding network or water molecule was found in 1. The thermodynamic stability of the new complexes was investigated by using thermogravimetric analysis (TGA). The water-free hexanitratolanthanate ionic liquids are thermal and moisture stable. Four complexes, namely complexes 8-11, were found to be ionic liquid crystals by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). They all present smectic A liquid-crystalline phase.

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Energetic Ionic Liquids based on Lanthanide Nitrate Complex Anions

Tao

Huang

Boatz

et al. 2008

Chemistry A European J

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Energetic ionic liquids based on anionic lanthanide nitrate complexes Cat(+) (3)[Ln(NO(3))(6)](3-), where Cat(+) is guanidinium, 4-aminotriazolium, 4-amino-1-methyltriazolium, 4-amino-1-ethyltriazolium, 4-amino-1-butyltriazolium, 1,5-diaminotetrazolium, and 1,5-diamino-4-methyltetrazolium, were prepared. The hexanitratolanthanate (-cerate) salts with the last two cations, which are the first CO-balanced energetic ionic liquids that are stable to hydrolysis and air, have impact sensitivities of about 27 J. These ionic liquids were obtained by an environmentally friendly, simple method using nitrate-containing precursors. All salts were fully characterized by IR and NMR spectroscopy, elemental analysis, and determination of thermal stability, phase behavior, density, and water content. According to theoretical calculations, these new compounds have potential as propellants.

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Isotropic nuclear magnetic resonance shifts in ion-paired systems. Penta- and hexanitratolanthanate(III) complexes

Cited by 33 publications

References 0 publications

Complexes of Lanthanoid Nitrates with 15‐Crown‐5 and 18‐Crown‐6 Ethers

Complexes of Lanthanoid Nitrates with 15‐Crown‐5 and 18‐Crown‐6 Ethers

Water‐Free Rare‐Earth‐Metal Ionic Liquids/Ionic Liquid Crystals Based on Hexanitratolanthanate(III) Anion

Energetic Ionic Liquids based on Lanthanide Nitrate Complex Anions

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