Through-bond and through-space effects on proton chemical shifts. The magnetic anisotropy effects of freely rotating -XY3 groups upon distant protons

A general expression is presented for calculating the contributions of the magnetically anisotropic X-Y bonds of freely rotating -XY₃ groups to the shielding of protons of a freely rotating methyl group elsewhere in the same molecule. The expression can also be modified to calculate (a) the anisotropy contribution of a freely rotating -XY₃ group to the shielding of a fixed proton and (b) the contribution of a fixed anisotropic X-Y bond to the shielding of a freely rotating methyl group. Application is made to calculate the contribution of magnetic anisotropy changes, when a hydrogen atom is replaced by a methyl group, to the aryl and methyl proton chemical shifts of the methylbenzenes relative to benzene and toluene, respectively. Although the contribution of magnetic anisotropy is not negligible it is insufficient to account for the observed shifts. This conclusion applies also to the acetylenic proton chemical shifts of some methyl derivatives of acetylene. Some comments are made on the values of magnetic anisotropy obtained by the N.M.R. method.     

Dependence of NMR isotropic shift averages and nuclear shielding tensors on the internal rotation of the functional group X about the C-X bond in seven simple vinylic derivatives H2C=CH-X

The ‘Gauge Including Atomic Orbitals’ (GIAO) approach is used to investigate the question of intramolecular rotation. Ab initio GIAO calculations of NMR chemical shielding tensors carried out with GAUSSIAN 94 within the SCF-Hartree-Fock approximation are described. In order to compare the calculated chemical shifts with experimental ones, it is important to use consistent nuclear shieldings for NMR reference compounds like TMS. The influence of rotating functional groups X=CH₃, CHO, NO₂, NH₂, CONH₂, COOH or C₆H₅ on the shielding tensors in seven vinylic derivatives H₂C=CH-X is studied; the molecules are propene, acrolein, nitroethylene, ethyleneamine, acrylamide, acrylic acid and styrene. We observe a marked dependence of nuclear shielding and chemical shift on the torsional movement. Different Boltzmann averages over the conformational states are considered and compared for gas phase, liquid and solid state NMR. Their applicability to model cases for rigid or freely rotating molecules and for fixed molecules (e.g. polymers or proteins) with rapidly rotating groups is discussed and simple calculation models are presented. On the basis of this work it can be concluded that intramolecular rotation clearly affects the observed averages. Effects of up to 2 ppm have been observed for isotropic chemical shifts, and up to 17 ppm difference have been observed for individual tensor components, for example, of the carboxylic ¹³C atom in acrylic acid. The variation of the shielding tensor on a nucleus in a fixed molecular backbone resulting from an attached rotating group furthermore leads to a new relaxation mechanism by chemical shift anisotropy.     

Proton shielding function for hydrogen chloride

For a diatomic molecule the nuclear shielding constant σ(ξ) of either nucleus can be expanded as a power series in the relative displacement from equilibrium ξ. Thus the nuclear shielding function is

where ξ=(r-r _e)/r _e with r the actual bond length and r _e the equilibrium bond length. The σ_e ⁽ⁱ⁾ are molecular parameters. By experimental observation of the temperature dependence of the proton magnetic shielding of hydrogen chloride gas it is possible, after allowing for intermolecular effects, to obtain the values σ_e ⁽⁰⁾=32·48 (±0·33) p.p.m. and σ_e ⁽¹⁾=-100 (±24) p.p.m. for the coefficients of the proton shielding function. Using this data it is possible to show that the isotope shift between H³⁷Cl and H³⁵Cl is about 0·001 p.p.m. By a comparison with earlier results for molecular hydrogen it would appear that in some instances differences in vibrational and rotational averaging may alter chemical shifts between different compounds by amounts considerably larger than the experimental error in chemical shift measurement.     

Calculation of proton N.M.R. chemical shifts by means of a finite perturbation method

The magnetic shielding effect due to neighbouring carbon atoms through the diamagnetic and paramagnetic terms is calculated by means of a finite perturbation method in cooperation with a semi-empirical INDO molecular orbital method. The behaviour of the components of the shielding tensor arising from 2s and 2p orbitals centred on a neighbouring carbon is shown as a function of the distance, R, between the proton considered and the carbon. It is pointed out that the treatment by Pople and McConnell in the calculation of the proton chemical shift must be used carefully in unsaturated hydrocarbons, because some of the contributions from a neighbouring carbon do not show an R ^-3 dependence but an R ^-2 dependence. It is also shown that the gross trend of the observed proton chemical shifts in hydrocarbons is reproduced fairly well in the present calculation.     

1H and 13C NMR Spectral Study of Some 2r-Aryl-6c-phenylthian-4-ones,Their 1-Oxides and 1,1-Dioxides

ABSTRACT

Four 2r-aryl-6c-phenylthian-4-ones 1b?1e and their 1-oxides 2b?2e and 1,1-dioxides 3b?3e have been newly synthesized. ¹H and ¹³C NMR spectra have been recorded for all these compounds and 2r,6c-diphenylthian-4-one 1-oxide 2a. ¹³C NMR spectrum has been recorded for the sulfone 3a of 1a. For selected compounds ¹H-¹H COSY, HSQC, HMBC, and NOESY spectra have been recorded. The vicinal proton–proton coupling constants suggest that in all these compounds, the heterocyclic ring adopts chair conformation with equatorial orientations of the aryl and phenyl groups. Proton and carbon chemical shifts suggest that in the sulfoxides, the S=O bond is axial and enhances the J _aa value by some special effect. The S = O bond causes a significant upfield shift even on carbons without hydrogens. Significant solvent shifts also were observed.     

High resolution hydrogen resonance spectra of some substituted ethylenes

The olefinic proton resonance spectra of a number of mono- and 1, 2 di-substituted ethylenes have been analysed as AB, ABC or ABX systems to obtain the coupling constants and chemical shifts. The values of J _trans (range observed 13·7 to 18·0 c/s in 14 compounds) were significantly larger than J _cis in similar molecules. The values of J _cis (range observed 6·5 to 12·3 c/s in 8 compounds) are abnormally large when the olefinic bond is conjugated to an aromatic ring. Coupling between adjacent protons in an olefinic methylene group (J _gem) is much smaller, and sometimes negative. The shielding of the lone vinyl proton in mono-substituted ethylenes is smaller than that of the methylene group and in two cases (the vinyl group directly bonded to an oxygen atom) the difference is so great as to give an approximation to the ABX condition, so that the methylene protons appear to be shielded to an unusually large extent.     

Proton magnetic resonance in four-coordinated ferrous porphyrins

The N.M.R. spectra of ferrous four-coordinated octaethylporphyrin, deuteroporphyrin IX dimethylester, meso-tetraphenylporphin and mesotetra(αααα-o-pivalamidophenyl)porphin (the so-called ‘picket fence’ porphyrin) show that these paramagnetic complexes are in the same spin state in non-polar solvents. The isotropic paramagnetic shifts have been analysed using fluorine substituted tetraphenylporphins as probes for the estimation of the pseudocontact contribution to the observed shifts. The anisotropy of the pseudocontact interaction and the distribution pattern of the contact hyperfine interaction suggest that the spin state of these complexes corresponds to S=1. The electronic relaxation time for this configuration is very short, (T ₁=5 × 10^-13s), enabling the observation of high resolution spectra for these axially non-coordinated ferrous prophyrins.     

Transmission of polar substituent effects across the cubane ring system: 19F substituent chemical shifts (SCS) of 4‐substituted (X) cub‐1‐yl fluorides revisited

¹⁹F NMR shieldings of 4‐substituted (X) cub‐1‐yl fluorides ( 4 ) for a set of substituents (X?H, NO₂, CN, NC, CF₃, COOH, F, Cl, HO, NH₂, CH₃, Si(CH₃)₃, Li, O^? and NH) covering a wide range of electronic substituent effects were calculated using the DFT‐GIAO theoretical model. The level of theory, B3LYP/6‐311+G(2d,p), provided ¹⁹F substituent chemical shifts (SCS) in good agreement with experimental values where known. By means of NBO analysis, various molecular parameters were obtained from the optimized geometries. Linear regression analysis was employed to explore the relationship between the calculated ¹⁹F SCS and polar field, resonance and group electronegativity substituent constants (σ_F, σ_R and σ_x, respectively) and also the NBO derived molecular parameters (fluorine natural charges (Q_n), electron occupancies on fluorine of lone pairs (n_F) and occupation number of the C? F antibonding orbital (σ_CF*)). The key determining parameters appear to be n_F and σ_CF*(occup). Both factors are a function of the electrostatic field influence of the substituent (σ_F effect) but are counteractive in their influence on the shifts. No evidence for a significant resonance effect influence on the shifts could be identified. Copyright © 2009 John Wiley & Sons, Ltd.     

Anisotropies in carbon-13 chemical shift tensor,H-C-H bond angles and the signs of the coupling constants in 13CH3I, 13CH3Br, 13CH3Cl

A pulsed fast Fourier transform N.M.R. spectrometer is used to investigate the temperature dependence of the ¹³C chemical shifts in the nematic liquid crystal solutions of the following halides: ¹³CH₃I, ¹³CH₃Br, ¹³CH₃Cl. The H-C-H bond angles are accurately measured in this investigation from proton magnetic resonance studies. The signs of the coupling constants D _13CH , D _HH, J _13CH and the ordering parameter have been assigned to be all positive. The ¹³C magnetic shielding anisotropy is found to become more positive with the increasing electronegativity of the halogen substituents. The values of the anisotropies are: Δσ = σ _∥ - σ _⊥ = - 101 ± 15 p.p.m. (¹³CH₃I), - 10 ± 5 p.p.m. (¹³CH₃Br), 22 ± 5 p.p.m. (¹³CH₃Cl). Results for Δσ obtained from the slope of σ_n versus S ₃₃ agree with those obtained from the nematic-isotropic phase subtraction method.     

Solvent Dependence of H-F Coupling Parameters in Fluorobenzene

Solvent dependence of NMR spectral parameters has been the object of considerable interest in recent years (see Ref. 1 for a brief summary). More recently attention has been devoted to the solvent dependence of NMR parameters in fluorine-containing compounds. In their investigation of fluorobenzene, Mohanty and Venkateswarlu observed the effect of solvents on the proton and fluorine chemical shifts, but did not report any dependence of the H-K or H-F couplings on the solvent medium.² For 1,2-dichlorofluoroethylene Bell and Danyluk found a linear correlation between the directly bonded ¹³C-H and ¹³C-F couplings and the H-F couplings.³ These results, along with linear correlations between the ¹³C-H (or ¹³C-F) coupling and the proton (or fluorine) chemical shift, led to the inference that the medium effect acts to change the coupling parameters and shieldings by a similar mechanism.     

Influence of Aprotic Solvents on the Transmission of Anomalous Substituent Effects on 13C NMR Chemical Shifts at the Carboxyl Carbon (δco) in Meta-Substituted Benzoic Acids: A Strong Evidence for π-Polarization Mechanism

Anomalous (reverse) substituent-induced ¹³C nuclear magnetic resonance chemical shifts at the carboxyl carbon (δ_co) in meta-substituted benzoic acids have been studied for 11 substituents having varying electronic effects in 4 aprotic (nonhydroxylic) solvents of varying polarity by employing different dual substituent parameter models. The regression results for apolar aprotic solvents provide a strong evidence for through space π-polarization mode of transmission of reverse meta-substituent effects on the carboxyl carbon in benzoic acids. The results for dipolar aprotic solvents indicate significant specific solvation of π-polarized forms of the acids. The study showed further that an apolar aprotic solvent has a distinct preference over a dipolar aprotic one for investigating intrinsic substituent effects on chemical shifts in aromatic molecules.     

13C NMR Chemical Shift of β-Alkoxyvinylketones: II. Empirical Substituent Effects in β-Aryl-β-Methoxyvinyltrihalomethylketones

Evaluation by empirically derived equations for the substituent effect (α,β,γ,δ) on the ¹³C NMR chemical shifts for C-1, C-2, C-3 and C-4 in β-aryl-β-methoxyvinylhalomethylketones 1a-g to 2a-g [R³C(O)-CH=C(Ar)-OMe, where R³ = CCl₃, CF₃ and Ar = p-YC₆H₄ (Y = H, Me, MeO, F, Cl, Br, NO₂)], taking as reference the β-ethoxyvinyltrichloromethylketone (3), is reported. From the calculated values for the α,β,γ,δ effects for each substituent it was possible to estimate the chemical shift of each carbon of the compounds 1,2. The ¹³C chemical shifts of the C-1, C-2, C-3, C-4 of these compounds, can be estimated with good to rasoable precision: 84% of the calculated chemical shifts are found to be within ±1.0ppm, and 100% are found to be within ±1.5ppm. The Y-Effects on C-3 and C-4 are compared with carbon charge densities (qr).     

Mössbauer resonance investigations on the SnF2SnF4 system

The Mössbauer resonance spectra of the compounds isolated in the SnF₂SnF₄ system have been studied. The isomer shifts allowed the authors to locate the tin atoms in different chemical environments. The results have been correlated with the electronic structures of both oxidation states of tin and an estimate of the ionicities of the bonding orbitals has been given. For tin(IV) the quadrupole splitting can be explained by means of unequivalent neighboring fluorine atoms. For tin(II) it can be interpreted in terms of p-character and hybrid nature of bonding and non-bonding orbitals. A Goldanskii-Karyagin effect is observed for αSnF₂, Sn₃F₈ and Sn₇F₁₆.     

Stereochemical Effects on 1H Chemical Shifts in 2,3-Diazabicyclo[2.2.1]Hept-2-Ene (DBH), 2,3-Diazabicyclo[2.2.2]Oct-2-Ene (DBO) and Related Molecules

¹H-NMR spectra of DBH (1), DBO (2) and of the synthetic precursor to 1, 1,4-phenyl-2,4,6-triazatricyclo[5.2.1.0^2,6]heplanc-3,5-dione (3), were recorded in acetone-d₆ and C₆D₆ at 500 MHz. Assignment was aided by complete resolution of signals of 1 and 3 in C₆D₆ by aromatic solvent-induced shifts (ASIS). The effect of the change from phenyllriazolinedione to a diazene functional group on the chemical shifts of the exo,endo and syn,anti protons was investigated. The chemical shifts of the exo,endo protons of 1 are exceptionally sensitive to the functional group at the hetero substituted bridge in the DBH skeleton. However, the relative chemical shift of the syn,anti proton pair is independent of the nature of the functional group. The role of stereochemical effects on these chemical shifts is discussed.     

Correlations in 11B NMR spectra of dihalo derivatives of bis(1,2-dicarbollyl)cobalt(III)

In the ¹¹B NMR spectra of dihalo derivatives of bis(dicarbollyl)cobalt(III), we have identified a correlation between the ¹¹B NMR chemical shifts of substituted boron atoms and boron atoms found in other positions on the carborane skeleton. We have observed an increased shielding effect for fluorine atoms (compared with other halogens), manifested in an upfield shift of the ¹¹B NMR signals for antipodal and trans boron atoms. For the fluorine-containing compound Bu₄N⁺ [8,8′-F₂-3,3′-Co(1,2-C₂B₉H₁₀)₂]⁻, we propose the following sequence of electron density transfer: B(8) → {B(6) and B(10)} → B(4, 7). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 547–549 (cont.), July–August, 2006.     

Substituent effects in the Baeyer–Villiger reaction of acetophenones: a theoretical study

This paper reports the first complete theoretical study of substituent effects on the mechanism of the Baeyer– Villiger (BV) reaction in non‐polar solvents taking into account the lowest‐energy mechanism that has been proposed for this rearrangement which is non‐ionic and fully concerted. The BV reaction of p‐substituted acetophenones, p‐XC₆H₄COCH₃ (X = NO₂, CN, H, CH₃, OCH₃), with performic (PFA) and trifluoroperacetic (TFPAA) acids, catalyzed by formic (FA) and trifluoroacetic (TFAA) acids, respectively, using the MPWB1K functional and the 6‐311G(d,p) and 6‐311++G(d,p) basis sets, are studied. Solvent effects are taken into account by means of the PCM continuum model using dichloromethane as solvent. Electron‐donating substituents on the aryl group have a relatively small activation effect on the first step, but a pronounced activation effect on the second to the point of being able to change the rate‐determining step (RDS) of the reaction, as observed in the case of p‐methoxyacetophenone with TFPAA acids. After analyzing the changes in Gibbs free energy of activation, geometrical parameters, and charge distributions of the transition states (TSs), explanations are provided for the two distinct effects that substituents on the ketone have on the kinetics of the addition and migration steps of the BV oxidation. The effect of the acid/peracid pair used is also discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

KLL Auger and x-ray photoelectron spectra of phosphine,some phosphorus halides and the other hydrides isoelectronic with argon

KL₂L₃(¹D₂) Auger and 1s photoelectron energies have been measured for molecular hydrides isoelectronic with Argon (HCl, H₂S, PH₃ and SiH₄). In addition a detailed comparison of Auger and photoelectron shifts in a series of phosphorus halides (vs phosphine) has been undertaken using additional P_2p binding energies. The potential model is better able to predict 1s binding energy shifts with either ground state or relaxation corrected models than the 2p shifts. These latter values seem also to be reduced by shielding effects. In general, fluorides are better predicted than chlorides. Auger shifts correlate linearly(but not in a 1:1 relationship) with 1s photoelectron shifts throughout the isoelectronic series and also in the case of the phosphorus fluorides and phosphine. The two potential models, however, provide poor prediction of Auger shifts.     

Infrared absorptions and band widths of dilute solutions of CF3H in liquid Ar,N2, and Xe

The spectra of fluoroform (CF₃H) in the solvents Ar, N₂, and Xe have been obtained in the fundamental region (400–4000cm^?1) using a low temperature cryostat and a Fourier transform infrared spectrophotometer. Ab initio calculations at the HF/6-31G? level have been performed to obtain the calculated vibrational frequencies of the isolated CF₃H molecule and CF₃H in the presence of the solvents (Ar, N₂, and Xe). Comparison of the frequency shifts of CF₂H in solution with respect to the gas phase frequencies is made for the experimental and theoretical results. Lorentzian functions were used to fit the bands and obtain the wavenumber at the peak absorbance and the vibrational band widths. An analysis of the dynamics of relaxation has been made based on the infrared time correlation functions for three of the fundamental modes (ν₁, ν₃, and ν₄). Bandwidths, band moments, and relaxation times were obtained by appropriate fitting of the experimental correlation functions to theoretical models. In liquid argon, the temperature dependence of the second moment (M ₂) indicates that rotational relaxation explains the bandwidth of the ν₃ mode. For the ν₄ mode, the temperature dependence of M ₂ can be attributed to rotational relaxation if it is corrected with a Coriolis coupling term. The bandwidths of the ν₁ mode do not follow the rotational relaxation model, and probably vibrational relaxation is the dominant mechanism.     

A proton magnetic resonance investigation of some weak interactions in solution

The proton chemical shifts of cyclohexane, methyl iodide and iodoform are measured in a number of solvents. A complete calculation of the contribution to the solute proton chemical shift arising from the magnetic anisotropy of cylindrically symmetric solvents is given. Although the formula predicts the direction of the observed shifts, the observed values for non-polar solutes are always much larger than the calculated values. Some possible reasons for this are given and discussed.

The variation of the proton chemical shifts of the polar solutes methyl iodide and iodoform in aliphatic solvents are shown to agree with present theories of these effects. However, in aromatic solvents considerable deviations from the theoretical line are found and these are postulated to arise from solute solvent complexes in which the dipole axis of the solute lies along the hexagonal axis of symmetry of the benzene ring with the protons towards the ring. From the variation of the proton chemical shifts of methyl iodide and iodoform in toluene solution with temperature the following parameters were obtained. For the methyl iodide toluene complex the energy and entropy of formation are 1·3 ± 0·5 kcals/mole and 4·9 ± 0·4 e.u. respectively. For the iodoform toluene complex the corresponding values are 1·6 ± 0·2 kcals/mole and 6·4 ± 0·2 e.u.     

On the significant relativistic heavy atom effect on 13C NMR chemical shifts of β- and γ-carbons in seleno- and telluroketones

Unexpectedly large ‘Heavy Atom on Light Atom’ (HALA) effects have been found in ¹³C NMR (Nuclear Magnetic Resonance) chemical shifts of β- and γ-carbons of seleno- and telluroketones established by means of the high-accuracy calculations of ¹³C NMR chemical shifts in three representative real-life compounds, 2,2,5,5-tetramethyl-3-cyclopentene-1-selone, selenofenchone and 1,1,3,3-tetramethyl-1,3-dihydro-2H-indene-2-tellurone. The proposed computational scheme consists of the combination of accurately correlated coupled-cluster singles and doubles model approach for the non-relativistic calculations of shielding constants taking into account the solvent, vibrational and relativistic corrections, the latter obtained within the 4-component fully relativistic gauge-including atomic orbitals KT2 approach resulting in a very good agreement of the performed calculations with the experiment. The stereochemical dependence of the ‘long-range’ γ-HALA effect on the dihedral angle has been established in the model seleno- and telluroketones providing the largest shielding effect in the orthogonal orientation of the X=C_α–C_β–C_γ (X=Se, Te) moiety.