Use of silver trifluoroacetate together with lanthanide shift reagents for simplification of 1H NMR spectra of aromatic hydrocarbons

The equimolar mixtures of typical lanthanide shift reagents such as Eu(fod)₃, Pr(fod)₃ or Yb(fod)₃ with silver trifluoroacetate, previously used to induce paramagnetic shifts in the ¹H NMR spectra of alkenes, have been successfully applied to simple aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylenes. In benzene and p-xylene the signals of all the aromatic protons are shifted identically. In other substituted benzenes the magnitude of the induced shift depends on the distance between the proton and the substituents. In addition, the different behaviour of the signals of the methyl groups in meta-and para-xylene on the addition of the complex shift reagent allows the quantitative analysis of the two xylenes in their mixtures.     

trans–cis Isomerization of schiff's bases (N-benzylideneanilines) on addition of lanthanide shift reagents

Application of the lanthanide shift reagent Eu(fod)₃ to a series of benzylideneanilines causes isomerization of the stable trans form to the less stable cis form. A linear relationship was obtained between the % cis isomer with the mole ratio of Eu(fod)₃/substrate.     

tert-Butyl 7-cycloheptatrienylperacetate: The proton NMR spectrum and conformational analysis

The proton magnetic resonance spectrum of tert-butyl 7-cycloheptatrienylperacetate has been analyzed with the aid of the lanthanide shift reagents, Eu(fod)₃ Yb(fod)₃. Observation of the lanthanide-induced shifts showed, in conjunction with variable temperature studies establishing the conformational purity of the cycloheptatrienyl ring, that the peracetate substituent has a definite equatorial preference.     

NMR–Untersuchungen an Dicyclopentadienderivaten: I—1H-NMR: Anwendung von paramagnetischen Verschiebungsreagenzien (Eu(fod)3) zur Vereinfachung der Spektren exo/endo-isomerer Diole

The determination of the stereochemistry of a series of exo/endo-isomeric dihydro- and tetrahydro-dicyclopentadiene-9.10-diols (exo/exo or endo/endo), using Eu(fod)₃ for separation of the signals in their ¹H n.m.r. spectra, is discussed in detail. The paramagnetic shift values ΔEu determined for half-molar ratios Eu(fod)₃/diol allow an unambiguous stereochemical assignment of the diols with regard to exo/endo isomerism. The ΔEu quantities are correlated with the distance H_i…O-atom (R_i).     

Large lanthanide-induced chemical shifts in cobalt complexes of enethials (α,β-unsaturated thioaldehydes)

Eu(fod)₃-, Yb(fod)₃- and Pr(fod)₃-induced chemical shifts of the ‘thioaldehydic’ protons in enethial ligands complexed to a cobalt cyclopentadienyl group are unusually large and in the same direction (10–30 ppm downfield per mole of shift reagent per mole of substrate). The shifts of the protons induced by Eu(fod)₃ and Pr(fod)₃ in the enethial ligands show an alternation in sign on proceeding away from the sulfur atom. In contrast to the results with the fod reagents, the ytterbium and lanthanum shift reagents Yb(thd)₃ and La(thd)₃ caused only small shifts of protons in the 2-phenylpropenethial ligand. No induced shifts with the Eu or Pr reagents were observed for a cyclopentadienyl cobalt complex of dithioglyoxal. The induced shifts in these enethial complexes may be caused by varying blends of complex formation, contact and pseudocontact shifts. Caution is advised in assigning origins to lanthanide induced shifts in such organometallic systems.     

The proton magnetic resonance spectrum of 4-t-butyl-5, 6-dihydro-4H-pyran

The proton magnetic resonance spectrum of 4-t-butyl-5,6-dihydro-4H-pyran has been analyzed with the aid of the paramagnetic shift reagent Eu(fod)₃. All hydrogen-hydrogen spin-spin coupling constants are reported and a conformation is suggested which is consistent with these data.     

The configuration and conformation of the tricyclo[4.4.1.12,5]dodecan-11-ols determined by 1H NMR spectroscopy using the shift reagent Eu(fod)3

The isomeric tricyclo[4.4.1.1^2,5]dodecan-11-ols have been synthesized from the (6+4) cycloaddition product of tropone with cyclopentadiene. The configuration and conformation of each isomer was determined from the proton shift gradients induced in the olefinic proton signals in the ¹H NMR spectra of intermediate compounds by Eu(fod)₃.     

Eu(fod)3 binding on the 1H‐NMR spectra of bis(2′‐ethylbenzoate)ethylene glycol podands

The complexing and selective binding constants of Eu(fod)₃ with bis(2′‐ethylbenzoate)ethylene glycol podands having one to four oxyethylene groups was observed on their ¹H‐NMR spectra at 250 MHz and 295 K in CDCl₃. The Eu(fod)₃ interaction displayed the selective binding role of oxygen on H₂C–O–CH₂ backbones with referring the ¹H chemical shifts. The estimated equilibrium constants, K_a, of 1:1 ratio of interactions were in accordance with the Eu(fod)₃ ionic radii to bind the oxygen sites depending on the size and conformation of the esters. Esters having one or two ethyleneoxy groups gave mainly 2:2 complexes using ester sites. The minimum lanthanide‐podand ester distance displayed the maximum stability so that ester with four oxyethylene groups was found to bind the Eu(fod)₃ moderately, whereas ester with three oxyethylene groups showed a large induced chemical shift due to the stability of Eu³⁺ complexes with larger ethyleneoxy groups. Copyright © 2012 John Wiley & Sons, Ltd.     

Ir and pmr spectra of 2-aryl-4-thiazolidinones. III. Stereochemical analysis of 2-aryl-3-(2-pyridyl)-4-thiazolidinones

The long-range coupling through the sulphur atom observed in a number of 2-aryl-3-(2-pyridyl)-4-thiazolidinones suggests that the C₂ proton and one of methylene protons are in a cis 1,3 diequatorial relationship. Some additional information concerning the preferred orientations of the substituents in this system are given from Eu(fod)₃, [tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionato)]europium, induced shift data.     

Study on the synthesis of the lanthanide chelates of α′-(trifluoromethyl)polyfluoroalkyl β-diketones and their application as 1H NMR shift reagents

The synthesis of the lanthanide chelates of α′-(trifluoromethyl)polyfluoroalkyl β-diketones Ln {CF₃CF₂[CF₂OCF(CF₃)]_n COCHCOC(CH₃)₃}₃ [ 1 , n=1; Ln=Eu (1a) , Pr (1b) , Nd (1c) , Sm (1d) , Gd (1e) , Tb (1f) , Dy (1g) , Er (1h). 2 , n=2; Ln=Eu (2a) , Pr (2b) , Nd (2c) , Sm (2d) , Gd (2e) , Tb (2f) , Dy (2g) and Er (2h) ] was reported and the ¹H NMR shift properties were studied using alcohol, ketone, ether and amine as substrates. Compounds 1a, 1b, 2a and 2b induce shifts similar to that induced by Ln(fod)₃ (Ln=Eu, Pr). However compounds 1a and 2a are superior to Eu(fod)₃, because their ¹H signal shifts to higher field in the presence of substrate than that of Eu(fod)₃, does. For example, Δh for 1a and 2a is close to zero ppm in the presence of alcohol. A very satisfactory first order spectra can be obtained using 1a, 2a, 1b and 2b as ¹H NMR shift reagents. 1c, 1f, 1g, 2c, 2f and 2g produce upfield shifts, and 1h and 2h produce downfield shifts. 1c and 2c induce shifts smaller than that of 1b and 2b , whereas 1f, 1g, 1h, 2f, 2g and 2h induce very large shifts.     

Excitation Energy-Transfer Processes in the Sensitization Luminescence of Europium in a Highly Luminescent Complex

The excitation energy transfer (EET) pathways in the sensitization luminescence of Eu^III and the excitation energy migration between the different ligands in [Eu(fod)₃dpbt] [where fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and dpbt=2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine], exhibiting well-separated fluorescence excitation and phosphorescence bands of the different ligands, were investigated by using time-resolved luminescence spectroscopy for the first time. The data clearly revealed that upon the excitation of dpbt, the sensitization luminescence of Eu^III in [Eu(fod)₃dpbt] was dominated by the singlet EET pathway, whereas the triplet EET pathway involving T₁(dpbt) was inefficient. The energy migration from T₁(dpbt) to T₁(fod) in [Eu(fod)₃dpbt] was not observed. Moreover, upon the excitation of fod, a singlet EET pathway for the sensitization of Eu^III luminescence, including the energy migration from S₁(fod) to S₁(dpbt) was revealed, in addition to the triplet EET pathway involving T₁(fod). Under the excitation of dpbt at 410 nm, [Eu(fod)₃dpbt] exhibited an absolute quantum yield for Eu^III luminescence of 0.59 at 298 K. This work provides a solid and elegant example for the concept that singlet EET pathway could dominate the sensitization luminescence of Eu^III in some complexes.     

Effect of the Excitation of the 4f Shell of Eu(fod)3 on the Formation of Complexes with 1,10-Phenanthroline

The effect of the electronic excitation of the -diketonate Eu(fod)₃ (fod is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctanedione-3,5) on complexation with 1,10-phenanthroline (phen) in benzene solutions was studied. The excitation of the f–f transitions of Eu³⁺ increased the stability of the Eu(fod)₃ · phen complex, thus providing direct evidence for the involvement of the 4f shell of Eu³⁺ in chemical bonding. The thermodynamic parameters of complexation were determined. The temperature quenching of Eu(fod)₃ · phen luminescence was studied.     

Conformational Mobility of Substituted 2-Methoxychalcones under the Action of Lanthanide Shift Reagents

Various lanthanide shift reagents Ln(fod)₃ were found to affect the conformational composition of 2-methoxychalcones. Coordination of Yb(fod)₃ occurs mainly at the carbonyl oxygen atom of the substrate, while Eu(fod)₃ and shift reagents derived from other lanthanides coordinate substituted chalcones as bidentate ligands, giving rise to a secondary tetrachelate with the corresponding change of conformation of the substrate molecule. The possibility for chelation is determined by steric hindrances in the vicinity of the substrate coordination centers and concurrent coordination of other electron-donor groups present in the substrate molecule.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 51–56.Original Russian Text Copyright © 2005 by Turov, Bondarenko, Tkachuk, Khilya.     

NMR spectral studies: XIII—titanium tetrachloride-induced and lanthanide-induced shifts in the proton NMR spectra of β-lactams

2-Azetidinones which carry a proton each on C-3 and C-4 often pose a problem in the correct assignment of the resonances due to these protons; titanium tetrachloride has been shown to be an effective and reliable n.m.r. shift reagent to differentiate between these two protons on the basis of their different sensitivities to this reagent. A few compounds were also studied with Eu(fod)₃ and Pr(fod)₃ for the sake of confirmation.     

Influence of Excitation of the Lanthanide 4 fShell on Complexation with Organic Substrates in Solutions: 2. Isotope Effects in Complexation of Tris(heptafluorodimethyloctanedionato)europium(III) with Dimethyl Sulfoxide in Benzene Solutions

The effect of deuteration of dimethyl sulfoxide on the fluorescence quantum yield, temperature quenching of fluorescence, and its complexation with tris(heptafluorodimethyloctanedionato)europium(III) (Eu(fod)₃) in the ground and excited states was studied. It was found that excitation of f–ftransitions in Eu(III) increases the stability of Eu(fod)₃complexes with sulfoxides but has a very insignificantly influence on isotope effects. The deuterium effect is displayed to a small extent in altering the quantum yield and is accompanied by a decrease in the efficiency of temperature quenching of Eu(fod)^* ₃fluorescence.     

Détermination des configurations Z et E d'imines par RMP. Combinaison de l'étude directe et en présence d'Eu(fod)3

Analysis of NMR spectra of different cyclic and acyclic imines, together with those obtained with the lanthanide shift reagent Eu(fod)₃, allowed the characterisation of the syn-anti (Z-E) isomerism of these compounds. In one case, it was possible to demonstrate a syn-anti equilibration by adding Eu(fod)₃.     

Effect of 4f-shell excitation of Eu(fod)3 on its complex formation with alicyclic ketones

The complex formation of alicyclic ketones, viz., camphor, cyclohexanone, menthone, and cytisine, with the Eu(fod)₃ chelate (fod is 7,7-dimethyl-1,1,1,2,2,3,3-heptafluorooctane-4,5-dione) in the ground and excited states was studied by chemiluminescence and kinetic luminescence spectroscopy, respectively. The stability constants and thermodynamic parameters of complex formation were determined. An increase in the stability of the electron-excited complexes [Eu(fod)₃*·Ketone] is explained by the enhancement of the acceptor ability of the Eu³⁺ chelate due to an increase in the fraction of the covalent component caused by the involvement of 4f-orbitals. The results obtained give direct evidence for the effect of the 4f-shell excitation of Eu(fod)₃ on complex formation due to the involvement of f-electrons in the chemical bonds.     

The influence of excitation of the 4f-orbital of Eu(fod)3 on complex formation with adamantanone and anomalous enhancement of Eu3+ luminescence under the action of H2O and D2O molecules in toluene

The influence of excitation of the 4f-orbital of, β-diketonate Eu(fod)₃ (fod is heptafluorodimethyloctanedione) on the formation of the coordination bond with adamantanone (1) was studied by the nonradiative energy transfer technique. The kinetic parameters of fluorescence (FL) and the lifetime (τ) of the Eu³⁺ ion in toluene solutions were studied. The increase in the stability of the Eu(fod)₃·1 complex when f—f-transitions of the Eu³⁺ ion are excited is related to an increase in the acceptor capability of Eu(fod)₃ due to the increasing fraction of the covalent component determined by the participation of 4f-orbitals. An unexpected effect of enhancement of the Eu(fod)₃ fluorescence under the action of H₂O (D₂O) molecules in toluene solutions was observed. The effect is assumed to be caused by an increase in the negative inductive effect when outer-sphere associates with the fluorinated radical of β-diketonate are formed. The mechanisms of the influence of electron-donating inner-sphere ligands and outer-sphere associates on the quantum yield of fluorescence of Eu(fod)₃ are discussed.     

Nuclear magnetic resonance and stereochemistry of vincamone

The stereochemistry in solution of vincamone was deduced by proton magnetic resonance using the paramagnetic shifts reagent Eu(fod)₃. The lanthanide induced shift computer simulation suggests that, at room temperature, the indole group is nearly planar, the rings C and E assume the envelope conformation with N-4 and C-16 as flaps, the ring D is in the chair one and the ethyl side chain prefers a trans position with respect to C-15.     

1H NMR study of naphthoflavones with shift reagents

The complete assignment of the proton NMR spectra of several α-, β- and γ- naphthoflavones at 100 MHz using Eu(fod), and double resonance experi- ments has been carried out. The compounds were found to associate at the carbonyi oxygen, by analogy with flavones where complete structural assignment can be attained using Pr(fod)₃, at 60MHz. The three types of naphthoflavones can be distinguished by observation of the quantitative lanth- anide-induced shifts at H-3 and/or H-5, combined with their chemical shift values in the absence of shift reagent.