Experimental and Theoretical Evidence of Spin-Orbit Heavy Atom on the Light Atom 1H NMR Chemical Shifts Induced through H⋅⋅⋅I− Hydrogen Bond

Spin-orbit (SO) heavy-atom on the light-atom (SO-HALA) effect is the largest relativistic effect caused by a heavy atom on its light-atom neighbors, leading, for example, to unexpected NMR chemical shifts of ¹H, ¹³C, and ¹⁵N nuclei. In this study, a combined experimental and theoretical evidence for the SO-HALA effect transmitted through hydrogen bond is presented. Solid-state NMR data for a series of 4-dimethylaminopyridine salts containing I⁻, Br⁻ and Cl⁻ counter ions were obtained experimentally and by theoretical calculations. A comparison of the experimental chemical shifts with those calculated by a standard DFT methodology without the SO contribution to the chemical shifts revealed a remarkable error of the calculated proton chemical shift of a hydrogen atom that is in close contact with the iodide anion. The addition of the relativistic SO correction in the calculations significantly improves overall agreement with the experiment and confirms the propagation of the SO-HALA effect through hydrogen bonds.     

“Through-Space” Relativistic Effects on NMR Chemical Shifts of Pyridinium Halide Ionic Liquids

We have investigated, using two-component relativistic density functional theory (DFT) at ZORA-SO-BP86 and ZORA-SO-PBE0 level, the occurrence of relativistic effects on the ¹H, ¹³C, and ¹⁵N NMR chemical shifts of 1-methylpyridinium halides [MP][X] and 1-butyl-3-methylpyridinium trihalides [BMP][X₃] ionic liquids (ILs) (X=Cl, Br, I) as a result of a non-covalent interaction with the heavy anions. Our results indicate a sizeable deshielding effect in ion pairs when the anion is I⁻ and I₃⁻. A smaller, though nonzero, effect is observed also with bromine while chlorine based anions do not produce an appreciable relativistic shift. The chemical shift of the carbon atoms of the aromatic ring shows an inverse halogen dependence that has been rationalized based on the little C-2s orbital contribution to the σ-type interaction between the cation and anion. This is the first detailed account and systematic theoretical investigation of a relativistic heavy atom effect on the NMR chemical shifts of light atoms in the absence of covalent bonds. Our work paves the way and suggests the direction for an experimental investigation of such elusive signatures of ion pairing in ILs.     

A carbon-13 NMR study of the ion pair structure of the dibenzo[b,f]pentalene dianion

The ¹H and ¹³C NMR chemical shifts of dibenzo[b, f]pentalene and its 5,10-dimethyl derivative are presented and compared with those of the corresponding dilithium dianions. As probed by the relative ¹³C NMR chemical shifts, the charge distribution within the dianion system is clearly dependent on the actual ion pair state. This condition is demonstrated by varying the solvent and temperature. The polarization of charge towards the pentalene carbons, i.e. the preferred cation positions, is observed on going to tight ion pair conditions. Further support for this model is gained from ⁷Li NMR. The limitations of the use of ¹H and ¹³C NMR chemical shifts to measure charge distributions within anion systems are discussed.     

A 1H and 13C NMR study of methoxyretinoids. Spectral assignment and determination of configuration

A number of modified retinals and retinoic esters carrying one or two methoxy groups or one methoxy and one methyl group on the polyene chain were investigated by ¹H and ¹³C NMR spectroscopy. Spectral assignments were made from homo- and selective ¹³C{¹H} hetero-decoupling experiments and from chemical shift comparisons. The configurations of the polyene double bonds were derived from vicinal H,H coupling constants, from ¹H and ¹³C chemical shifts and by measuring nuclear Overhauser enhancements. It is found that all double bonds with no additional substituents occur in the trans (E) and all methoxy-substituted double bonds in the cis (also E) configuration. Double bonds carrying methyl groups give rise to both cis (Z) and trans (E) isomers.     

Carbon-13 NMR spectra of monosubstituted pyrazines

Carbon-13 NMR chemical shifts and one-bond carbon–hydrogen coupling constants have been obtained at 15·09 MHz. The trends in the carbon chemical shifts obtained for the pyrazines parallel those of monosubstituted benzenes and 2-substituted pyridines, except for the direct effect of substitution where the pyrazines resemble pyridines not benzenes. The substituent effects on the ¹³C NMR spectra are generally quite similar to those in the ¹H NMR spectra. The ¹³C NMR spectrum of the tautomeric hydroxypyrazine has been compared with the ¹³C NMR spectra of 2-, 3- and 4-hydroxypyridines. Hydroxy compounds that can exist as a cyclic amide show a large meta substituent effect on the chemical carbon shift.     

A nuclear magnetic resonance study of three isomeric dinaphthothiophenes

The ¹H and ¹³C NMR spectra of three isomeric dinaphthothiophenes are recorded. Chemical shift assignments were made on the basis of substituent chemical shift (SCS) effect arguments, coupling considerations, proton—proton auto-correlated homonulcear (COSY) two-dimensional spectroscopy, and proton—carbon heteronuclear correlation (HETCOR) two-dimensional spectroscopy. Some previously published ¹H chemical shifts and coupling constants are compared with our data and some divergences are noted.     

1H and 13C chemical shift data of four peracetylated triglucoses. Application of two-dimensional techniques

¹H and ¹³C chemical shifts are reported for four peracetylated triglucoses. Assignments are based on the recently proposed two-dimensional Relayed Coherence Transfer Technique. The chemical shift data were obtained from conventional one-dimensional NMR spectra.     

NMR study of the spatial structure of synthetic pyrethroids

The spatial isomers of the new synthetic analogs of ethyl permithrinic ether and permethrin were investigated by NMR (¹H, ¹³C, DEPT (distortionless enhancement by polarization transfer), COSY (correlation spectroscopy), CHCORR (heteronuclear (C, H) shift correlation spectroscopy), ROESY (rotating-frame Overhauser effect spectroscopy)). Several tendencies were revealed in the ¹H and ¹³C chemical shifts of the α atoms of the substituents in the 2nd and 3rd positions of the cyclopropane ring. For substituents cis-orientated relative to the ester group, the spectra show a paramagnetic shift of the ¹H signals and the diamagnetic shift of the ¹³C signals relative to the trans-orientated substituents. The ¹H and ¹³C chemical shifts of the α atoms of the substituents in the 2nd and 3rd positions of the cyclopropane ring permit an unambiguous determination of the stereochemistry of ethyl permethrinic ether and permethrin analogs.     

Effect of the orientation of substituents on the chemical shifts of 13C. IV—13C NMR spectra of N,N-diisopropylamides and -thioamides

N,N-diisopropylamides and -thioamides show hindered rotation around the N? CH bonds, and the presence of mixtures of conformational isomers can be demonstrated at temperatures below 273 K in solution. ¹H and ¹³C NMR spectra of these conformers are measured and assigned. The ¹³C data serve to study through-space effects on ¹³C chemical shifts, which strongly depend on the conformations of the isopropyl groups. For amides, a through-space shielding of the N-methine carbons is found to exist only for conformers in which the methine hydrogen atom is spatially close to the oxygen atom. Chemical shift differences between amides and thioamides can be rationalized in terms of through-bond and through-space contributions, and serve for a better understanding of the shift differences in N,N-dialkylamides and -thioamides.     

NMR chemical shifts as a tool to analyze first principles molecular dynamics simulations in condensed phases: the case of liquid water

We present (1)H NMR chemical shift calculations of liquid water based on first principles molecular dynamics simulations under periodic boundary conditions. We focus on the impact of computational parameters on the structural and spectroscopic data, which is an important question for understanding how sensitive the computed (1)H NMR resonances are upon variation of the simulation setup. In particular, we discuss the influence of the exchange-correlation functional and the size of the basis set, the choice for the fictitious electronic mass and the use of pseudopotentials for the nuclear magnetic resonance (NMR) calculation on one hand and the underlying Car-Parrinello-type molecular dynamics simulations on the other hand. Our findings show that the direct effect of these parameters on (1)H shifts is not big, whereas the indirect dependence via the structural data is more important. The (1)H NMR chemical shifts clearly reflect the induced structural changes, illustrating once again the sensitivity of (1)H NMR observables on small changes in the local chemical structure of complex hydrogen-bonded liquids.     

The study of longifolene by two-dimensional NMR spectroscopy

The complete assignment of the ¹³C NMR spectrum of longifolene was achieved from double quantum coherence measurements, while combined evaluation of a ¹H? ¹³C heteronuclear chemical shift correlation diagram and a homonuclear ¹H J-resolved diagram provided all proton chemical shifts. Conformational information on the seven-membered ring of the tricyclic sesquiterpene was obtained from proton chemical shift considerations.     

1H, 13C and 15N NMR spectral analysis of substituted 1,2,3,4‐tetrahydro‐pyrido[1,2‐a]pyrimidines

The NMR spectroscopic data of a series of thirty‐four 3‐acylpyrido[1,2‐a]pyrimidinium salts are analyzed, which were prepared as either perchlorates or chlorides. Methyl group substituted 3‐aroyltetrahydropyrido[1,2‐a]pyrimidines with the methyl substituent in positions 6, 8 and 9 as well as both in positions 6 and 8 were investigated bearing various aroyl substituents. Unequivocal assignment of all resonances was achieved via two‐dimensional ¹H,¹H‐COSY measurements, ¹H,¹³C and ¹H,¹⁵N HSQC as well as HMBC experiments, and important diagnostic CH and NH couplings in the heteroaromatic ring system are evaluated. The influence of the methyl substituents was analyzed on the proton, carbon and nitrogen shifts. A significant effect of the counter ion on some chemical shifts of the nuclei under discussion of the pyridopyrimidines is found, allowing the indirect detection of the anion, which is confirmed by direct measurement of the ³⁵Cl nucleus of the perchlorates. Copyright © 2013 John Wiley & Sons, Ltd.     

Comparison of the effects of the intra- and intermolecular hydrogen bonds C-H...X (X = O,N) in1H and13C NMR spectra

A similarity between manifestations of the effects of the intra- and intermolecular hydrogen bonds C-H...X (X = O, N) in¹H and¹³C NMR spectra has been shown. A correlated increase in the direct spin-spin coupling constant¹³C—¹H and the chemical shifts of the proton participating in the interaction has been observed.Translated fromIzvestiya Akademii Nauk. Seriyo Khimicheskaya, No. 5, pp. 1205–1207, May, 1996.     

Multinuclear two-dimensional NMR: Assignments of natural abundance polypeptide 13C, 1H and 15N chemical shifts and demonstration of isomer interconversion

The polypeptide carbobenzoxy-glycyl-L -prolyl-L -leucyl-L -alanyl-L -proline (0.2 M in DMSO-d₆) was investigated using ¹³C, ¹H and ¹⁵N NMR in natural abundance at 4.7 tesla. The existence of cis–trans-Gly-Pro and -Ala-Pro bonds permits up to four isomers, and all four were observed (in a 60:30:7:3 ratio). ¹³C shifts of the proline β-CH₂ resonances are consistent only with the 60% form being trans–trans. The 30% form is either trans–cis or cis–trans (order as above) and was tentatively assigned as cis-trans on the basis of relaxation behavior. Refocused INEPT studies aided the ¹³C assignments. The ¹⁵N data were obtained using both NOE and INEPT excitation, with signals evident for the three major isomers. The spectra were analysed by starting from the ¹³C data, which were assigned based on known regularities in peptide spectra. A ¹³C? ¹H heteronuclear two-dimensional chemical shift correlation experiment allowed direct assignment of proton shifts for major and minor isomers. The NH proton shifts were assigned by running a homonuclear two-dimensional chemical shift correlation experiment and noting the correlation with the previously assigned α-CH protons. The ¹⁵N resonances were then assigned from a ¹⁵N? ¹H heteronuclear two-dimensional chemical shift correlation experiment, relating the ¹⁵N signals directly to the NH proton resonances. Isomer interconversion between the two major isomers was demonstrated by performing a magnetization transfer homonuclear 2D experiment. Off-diagonal intensity was noted relating the major and minor isomer alanine NH proton, as well as for the major and minor isomer leucine NH protons.     

Effects of different GIAO and CSGT models and basis sets on 2-aryl-1,3,4-oxadiazole derivatives

The direct molecular structure implementations of the gage-including atomic orbital (GIAO), individual gages for atoms in molecules (IGAIM) and continuous set of gage transformations (CSGT) methods for calculating nuclear magnetic shielding tensors at both the Hartree-Fock (HF) and density functional (B3LYP) levels of theory with 6-31G(d), 6-311G(d), 6-31++G(d,p), 6-311++G(d,p), and 6-311++G(df,pd) basis sets are presented. Dependence on the ¹H and ¹³C NMR chemical shifts on the choice of method and basis set have been investigated. Also, these chemical shifts of 2-aryl-1,3,4-oxadiazoles 5a–g have been performed related to dihedral angles (C4–C3–C2–O) of two conformers. The optimized molecular geometries and ¹H and ¹³C chemical shift values of 2-aryl-1,3,4-oxadiazoles 5a–g in the ground state have been obtained. The linear correlation coefficients of ¹³C NMR chemical shifts for these molecules were given. The new nuclear magnetic shielding tensors of tetramethylsilane (TMS) were calculated. The data of 2-aryl-1,3,4-oxadiazole derivatives display significant molecular structure and NMR analysis. Also, these provide the basis for future design of efficient materials having the 1,3,4-oxadiazole core.     

Frequency dependence of nuclear magnetic resonance parameters in poly(methyl methacrylate)

Using 26 NMR spectrometers, the Research Group on NMR, the Society of Polymer Science, Japan observed the ¹H NMR chemical shift, resolution, and signal intensity; ¹³C NMR chemical shift, resolution, and signal intensity; the effect from initiator fragment signal; ¹H spin-lattice relaxation times; ¹³C spin-lattice relaxation times; and ¹³C nuclear Overhauser enhancement of radically polymerized poly(methyl methacrylate). Excellent reliability was found after comparison between the data from different spectrometers. Molecular motion of this polymer was analyzed with a term of 3τ model.     

Electron density distributions in substituted 2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-dienes studied by NMR spectroscopy

The signals in the¹³C NMR spectra of 2,3,4,5-tetraphenyl-1-germacyclopenta-2,4-dienes (R¹=R²=H, Me,cyclo-C₃H₅, SiMe₃, SnMe₃, R¹=Me, R²=H, Cl) were completely assigned using 2D NMR spectroscopy. The pattern of the variation of the chemical shifts in the¹³C NMR spectra indicates that the effects of substituents R¹ and R² on the heterocycle and on the phenyl groups are of inductive rather than mesomeric origin and include the direct through-space polarization of bonds (field effect). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1962–1965, November, 1997.     

The Effect of C4H and C5H on the Microstructure of Aqueous Solutions of 1‐Alkyl‐3‐methylimidazolium Tetrafluoroborate Ionic Liquids

As is well‐known, the C2?H proton of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([Emim]BF₄) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim]BF₄) has a strong ability to form hydrogen bonds. The purpose of this work is to evaluate the effect of the interactions of the C4?H and C5?H protons on the microstructure of [Emim]BF₄ and [Bmim]BF₄ with water by using ¹H NMR spectroscopy. The differences between the relative ¹H NMR chemical shifts of C2?H, C4?H, and C5?H and between the interaction‐energy parameters obtained from these chemical shifts are minor, thus suggesting that the interactions of C4?H and C5?H may have a considerable effect on the microstructure. To confirm this, the viscosities of the systems are estimated by using the interaction‐energy parameters obtained from the ¹H NMR chemical shifts of the three studied aromatic protons and water, showing that the interactions of C4?H and C5?H also play an important role in the microstructure.     

Carbon-13 nuclear magnetic resonance studies on dichloropyridoquinolines

Carbon-13 NMR chemical shifts are reported for six angular and one linear dichloropyridoquinolines in CDCl₃. The chemical shift assignments have been made using model compounds, fully coupled spectra, selective proton decoupling and results from lanthanide shift studies. Chlorine substituent effects are compared to those reported for chloroquinolines. The effect of the heteroaromatic nitrogen atoms on ¹³C? ¹H coupling constants in these polycyclic systems are compared to those reported for pyridine systems.