Theoretical study of spin-spin coupling constants in thecis-enol forms of β-dicarbonyl compounds

The values of the spin-spin coupling constant J(CH) of the bridging proton in the cis-enol forms of -dicarbonyl compounds have been calculated with consideration of the one-dimensional distribution functions of the proton. The results have been compared with the experimental data obtained in the present investigation. The dependence of the spin-spin coupling constants considered on the parameters of the potential of the intramolecular hydrogen bond has been discussed.Institute of Bioorganic Chemistry, Academy of Sciences of the Belorussian SSR, M. V. Lomonosov Moscow State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 2, pp. 84–87, March–April, 1991.     

Empirical analysis of vicinal proton-proton spin-spin coupling constants from the classic and modified Karplus equations in the γ-piperidone series

We present a novel approach for empirical parametrization of the Karplus equation, based on differentiation not only according to the class of compound but also according to the type of spin-spin coupling constant. In the case of -piperidones, this approach allows us to satisfactorily predict all the vicinal proton-proton spin-spin coupling constants, in contrast to previously proposed modified Karplus equations.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1566–1574, July, 1992.     

Can changes in one-bond spin-spin coupling constants in acids be related to gas-phase proton affinities of bases?

Ab initio EOM-CCSD calculations have been carried out in search of acids with one-bond spin-spin coupling constants which could serve as probes of molecular basicity upon complex formation. Only 1J(F-H) and 1J(B-Li) in complexes F-H...Y and H2B-Li...Y, respectively, are able to differentiate among the protonation energies of bases containing Y. Changes in 1J(F-H) upon complex formation are related to the protonation energies of bases, but only when these energies are about 200 kcal/mol or greater. On the other hand, changes in 1J(B-Li) upon complexation are related to base protonation energies in the range between 100 and about 190 kcal/mol. Thus, these two one-bond coupling constants 1J(F-H) and 1J(B-Li) are complementary probes. For the first time, the computed NMR property of a gas-phase one-bond spin-spin coupling constant has been related to the experimental gas-phase thermodynamic property of proton affinity.     

Structural trends of 77Se?1H spin–spin coupling constants and conformational behavior of 2‐substituted selenophenes

Experimental measurements and second‐order polarization propagator approach (SOPPA) calculations of ⁷⁷Se? ¹H spin–spin coupling constants together with theoretical energy‐based conformational analysis in the series of 2‐substituted selenophenes have been carried out. A new basis set optimized for the calculation of ⁷⁷Se? ¹H spin–spin coupling constants has been introduced by extending the aug‐cc‐pVTZ‐J basis for selenium. Most of the spin–spin coupling constants under study, especially vicinal ⁷⁷Se? ¹H couplings, demonstrated a remarkable stereochemical behavior with respect to the internal rotation of the substituent in the 2‐position of the selenophene ring, which is of major importance in the stereochemical studies of the related organoselenium compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Calculations of 13C NMR chemical shifts and F–C coupling constants of ciprofloxacin

Ciprofloxacin is a widely used fluoroquinolone antibiotic. In this work, a comprehensive evaluation of MP2 and DFT with different functionals and basis sets was carried out to select the most suitable level of theory for the study of the NMR properties of ciprofloxacin. Their relative predictive capabilities were evaluated comparing the theoretically predicted and experimental spectral data. Our computational results indicated that in contrast to the solid state, the molecule of ciprofloxacin does not exist as a zwitterion in gaseous state. The results of the calculations of the chemical shifts most close to the experimental were obtained with B3LYP/aug-cc-pVDZ. The F–C coupling constants were calculated systematically with different DFT methods and several basis sets. In general, the calculations of the coupling constants with the BHandH computational method including the applied in this work 6-311++G**, EPRII, and EPRIII basis sets showed a good reproducibility of the experimental values of the coupling constants.     

Ab initio calculations of oxygen nuclear quadrupole coupling constants and oxygen and silicon NMR shielding constants in molecules containing SiO bonds

Ab initio coupled Hartree—Fock perturbation theory (CHFPT) calculations employing large gaussian basis sets have been used to evaluate the electric field gradient at O, q^o, and the NMR shieldings at O and Si, σ^o and σ^Si, in the molecules SiO, SiO₂, Si₂O₂, H₂SiO, SiO⁻⁴₄, Si(OH)₄ and (H₃Si)₂O. Species containing Si bonded to three or fewer atoms have small NMR shieldings at both O and Si while those with four-coordinate Si have systematically larger O and Si shieldings. A significant positive correlation is observed between calculated O and Si NMR shieldings. Reduction of the SiO distance in SiO⁴⁻₄ and H₃SiOSiH₃ gives a significant reduction in the magnitude of q^o and a small increase in σ. Anisotropies in σ^Si are large for two- and three-coordinate Si (200–900 ppm) but for (H₃Si)₂O the σ^Si anisotropy is only ≈60 ppm. Anisotropies in σ^o are generally larger than those in σ^Si, with values larger than 200 ppm for both SiO⁻⁴₄ and (H₃Si)₂O. Values of q^o for SiO⁴⁻₄ and (H₃Si)₂O are in qualitative agreement with experimentally determined values for nesosilicates and SiO₂ polymorphs, respectively, but all the q^o values appear to be exaggerated at the Hartree—Fock level. Also, q^o values are not greatly different for the exotic species SiO, Si₂O₂, etc. compared to the typical silicate models SiO⁴⁻₄ and (H₃Si)₂O. Calculated isotropic chemical shifts yield good values for the Si chemical shift differences of SiF₄, SiO⁴⁻₄ and (H₃Si)₂O and for the O chemical shift difference of SiO⁴⁻₄ and H₂O. For SiO⁴⁻₄ the paramagnetic contribution to the Si shift, σ^pSi is dominated by contributions from the t₂ symmetry SiO bonding orbital and σ^pO is dominated by contributions from the t₂ symmetry O 2p non-bonding orbital.     

Excited Π states of divinyl chalcogenides and chalcophenes

Electron transitions in divinyl chalcogenides (CH₂=CHXCH=CH₂, where X is S, Se, or Te) have been analyzed using UV absorption spectra of dialkyl and alkyl vinyl chalcogenides. The following relations for the orbital energies are found: ^* < ^* < ^* < ^* for Te and ^* < ^* < ^* < ^* for S and Se. For chalcophenes, a correlation between the energy of the excited state (E ^*) of specific symmetry, the ionization potential (I) and the electron affinity (EA) is obtained:E ^*=const+(I+EA)/2. The electron affinity of divinyl chalcogenides is estimated. The correlation between the excited ^* states of divinyl chalcogenides and chalcophenes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 831–835, May, 1994.     

Hyperfine coupling constants of β-phosphorylated nitroxides: Subtle interplay between steric strain,hyperconjugation, and dipole-dipole interactions

Solvent effects in β-phosphorylated nitroxides show that nitrogen and phosphorus hyperfine coupling constants a_N and a_P, increase and decrease with increasing polarity, polarizity, and Hydrogen Bond Donor effects of solvents, respectively. In a series of articles, it was shown that the driving interaction controlling the change in a_P is the maximization of the N^+?—O^– … ???⁺PO^– dipole – dipole interaction. In this work, we show that the steric strain in spiro β-phosphorylated nitroxides affords the opposite trend for a_P, that is, a_P increases with increasing solvent properties features.     

Evalution of coriolis coupling constants for HCN...HF and their use in the estimation of vβ

Coriolis coupling constants have been determined for a hydrogen-bonded heterodimer (HCN...HF) for the first time. The set of ζ_ij values have been used in conjunction with B₀ and the l-doubling constant q_β to estimate the wavenumber of the low-frequency hydrogen-bond bending mode v_β.     

Copper-catalyzed oxidative C‒H,N‒H coupling of azoles and thiophenes

C?H, N?H coupling of azole and thiophene derivatives takes place in the presence of a catalytic amount of Cu(OAc)₂ and an additive. The reaction of azoles smoothly occurs with several amines and amides catalyzed by 20 mol % of Cu(OAc)₂–2PPh₃ and 4 equiv of NaOAc under O₂ or in the presence of Ag₂CO₃ under N₂. The coupling reaction leads to a facile synthesis of a N-substituted analogue of 2,5-diarylthiazole, which shows photoluminescent properties with extended π-conjugation. Spectroscopic characteristics of the obtained thiazole derivatives are discussed by measurements of UV–vis absorption and photoluminescent spectra. Under the reaction conditions using Ag₂CO₃ as an additive and Cu(OAc)₂–2PPh₃ as a catalyst, thiophene derivatives also react with 2-pyrrolidone to undergo C?H, N?H amidation.     

Ab initio study of the nuclear spin—spin coupling constants and magnetic shielding constants in silicon derivatives via the equations-of-motion method

Non-empirical equations-of-motion calculations of the nuclear spin—spin coupling constants and magnetic shielding constants in a representative series of molecules featuring siliconsilicon or siliconcarbon single, double and triple bonds are presented. The EOM results, which include the main portion of the electron correlation effects, are in resonable agreement with the available experimental data. On passing from single to double and triple bonding situation the pattern for the ¹J(SiY) parameters resembles that exhibited by ¹J(CY) in the structurally related carbocompounds, whereas an inversion in the relative position of the triply bonded atom is predicted in the case of the ²⁹Si resonance relative to the ¹³C sequence.     

Inelastic neutron scattering on an Mn10 supertetrahedron: assessment of exchange coupling constants, ferromagnetic spin waves and an analogy to the Hückel method

The synthesis, crystal structure and magnetic characterisation by magnetisation and inelastic neutron scattering (INS) of a mixed-valent Mn(10) supertetrahedral aggregate [Mn(III)(6)Mn(II)(4)(μ(4)-O)(4)(μ(3)-N(3))(3)(μ(3)-Br)(Hmpt)(6)(Br)]Br(0.7)(N(3))(0.3)·2MeOH·3MeCN (1) (H(3)mpt=3-methylpentan-1,3,5-triol) is reported. The magnetic core of the molecule can be described as an octahedron of six S=2 Mn(III) ions with four faces, each capped by a S=5/2 Mn(II) ion such as to form the supertetrahedron. Unlike most related complexes, the molecular symmetry is slightly reduced from approximately T(d) to C(3). The magnetic data reveal a total spin of S=22 in the ground state due to ferromagnetic exchange couplings within the molecule. The combined INS and magnetic data permits the accurate determination of the exchange coupling constants. Two types are found. The couplings between the Mn(III) ions in the inner octahedron are characterised by J(a)=18.4(3) K, whereas the couplings between the apical Mn(II) ions to the neighbouring Mn(III) ions are given by J(b)=7.3(2) K. The significantly larger coupling strength J(a) as compared to J(b), and the near-T(d) symmetry have profound consequences on the energy spectrum, which are discussed and carefully analysed. In particular, the observed INS spectra can consistently be reproduced by a simplified model in which the inner octahedron is replaced by one large spin of length S(0)=12. This model provides intuitive insight into the structure of the magnetic spectrum. Additionally, the magnetic excitations at low temperature are analysed within the frame of ferromagnetic linear spin-wave theory, which permits an analytical calculation of the energy levels. For ferromagnetic clusters, a close analogy to the Hückel method of electronic structure calculation can be drawn, which allows one to grasp the results of the spin-wave theory or the magnetic excitation spectrum, respectively, in a chemical language.     

Correlation of the 13C13C spin—spin coupling constants with the stretching force constants of single and double carbon—carbon bonds

Linear correlations between the spin—spin carbon—carbon coupling constants and the carbon—carbon stretching force constants for single and double bonds have been found through analysis of the available literature data. The corresponding equations are K^s_CC = 0.0344 J^s_CC+3.25 and K^d_CC = 0.180 J^d_CC−3.25 for single and double bonds respectively.     

The optimum contraction of basis sets for calculating spin–spin coupling constants

The previously proposed pcJ-n basis sets, optimized for calculating indirect nuclear spin–spin coupling constants using density functional methods, are re-evaluated for finding the optimum contraction scheme as a compromise between computational efficiency and minimizing contraction errors. An exhaustive search is performed for the H₂, F₂ and P₂ molecules, and candidates for optimum contraction schemes are evaluated for a larger test set of 21 molecules. Using the criterion that the contraction error should not exceed the basis set error relative to the basis set limit, the optimum contraction is defined for each basis set. The results show that it is difficult to contract basis sets for calculating spin–spin coupling constants to any significant degree without losing the inherent accuracy. The work provides guidelines for searching for optimum contraction schemes for other properties and/or at theoretical levels where a systematic search is impractical.     

¹H and ¹³C-NMR data of the simplest plumeran indole alkaloids isolated from Aspidosperma species

Indole alkaloids are the chemotaxonomic markers of the Aspidosperma genera. Those that have the simplest plumeran skeleton are classified as the precursors of biosynthetic routes and the intermediates for several synthetic reactions. This work aims to review the 1H and 13C-NMR data, up to 2011, describing the skeleton of 35 different plumeran indole alkaloids, from a group of 46 of them, and highlight the main spectral differences amongst them.     

Studies of silyl and germyl group VI species—III: The formation and identification of mixed silyl and germyl chalcogenides

Scrambling reactions between (Me₃M)₂E and (H₃M)₂E, where M = Si or Ge and E = S, Se or Te lead to the formation of mixed silyl and germyl chalcogenides of the type Me₃MEMH₃. All these species are identified by their ¹H NMR and mass spectral parameters. Evidence is presented for the formation of condensed species from the disproportionation of the selenogermanes.     

The carbon-13 chemical shifts and the analysis of the relaxation times T1 and long range 13C−1H coupling constants of quinoline and of 1-(X-quinolyl)ethyl acetate derivatives

The ¹³C chemical shifts and the ¹³C−¹H coupling constants of quinoline (1-(X-quinolyl)ethyl acetate derivatives (where X=−CH(OAc)CH₃ substituted at positions 2,4,5–8) are reported. Substituent chemical shift (SCS) effects for the ethyl acetate group are additive at all positions. A substantial upfield shift of 4.5 and 4.8 ppm was observed at C-4 and C-5, arising from the peri interaction of 5- and 4-ethyl acetate substituents respectively. A vicinal (peri) ³J CCCH coupling constant of approximately 5 Hz is observed between both C₅−H₄ and C₄−H₅. Carbon-13 relaxation times (T₁) and nuclear Overhauser enhancements (η) have been measured for quinoline and its derivatives, and the contributions of dipolar, T₁^DD, and spin rotation, T₁^SR, relaxation have been determined. Intramolecular dipole-dipole interactions are found to provide by far the most important spin-lattice relaxation mechanism whenever protons are bound directly to the carbons under investigation. Non-protonated ring carbons are relaxed by both DD and SR mechanisms. Anisotropic motion has an easily observable effect on the DD contribution to T₁, and can form the basis for spectral assignments, as in 1-phenylethyl acetate. Long-range ¹³C−¹H coupling constants were observed both between ring carbons and between ring carbons with ring side-chain hydrogens. These results have been used for the structure determination of the title compounds.     

Total synthesis and stereochemical reassignment of (±)-indoxamycin b

Revised version: The first total synthesis of indoxamycin?B leads to a stereochemical reassignment of the natural product. The synthetic route features an efficient carboannulation sequence to rapidly access the dihydroindenone system. Moreover, a series of Au(I) -catalyzed transformations served in the construction of the sterically congested core framework.     

13C-13C spin-spin coupling constants in structural studies: XLI. Stereochemical study on N-(polychloroethylidene)arenesulfonamides and N’-arylsulfonylformimidamides

The second-order polarization propagator approach (SOPPA) was used to calculate ¹³C-¹H, ¹³C-¹³C, and ¹⁵N-¹H coupling constants for a series of N-(polychloroethylidene)arenesulfonamides and N’-arylsulfonylformimidamides, and their configuration with respect to the C=N bond was determined by comparing the calculated data with the experimental values. All the examined compounds were found to exist in solution exclusively as the corresponding E isomers. The most favorable conformations and relative energies of the E and Z isomers in the gas phase were determined in terms of the second-order perturbation theory (MP2/6-311G**). N’-Arylsulfonylformimidamides are characterized by restricted internal rotation of the dialkylamino group about the C-N bond having an increased order. Original Russian Text ? K.A. Chernyshev, L.B. Krivdin, G.N. Rozentsveig, I.V. Ushakova, I.B. Rozentsveig, G.G. Levkovskaya, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 1, pp. 82–91. Dedicated to Full Member of the Russian Academy of Sciences G.A. Tolstikov on his 75th anniversary     

Stereochemical study of the sterically crowded phenylselanylalkenes by means of 77Se?1H spin–spin coupling constants

Stereochemical study of five sterically crowded phenylselanylalkenes obtained via the hydroselenation of either terminal or internal alkynes with benzeneselenol catalyzed by the nanosized Ni complexes has been carried out based on the experimental HMBC measurements and theoretical second order palarization propagator approach (SOPPA) calculations of their ⁷⁷Se? ¹H spin–spin coupling constants across double bond in combination with the energy‐based theoretical conformational analysis performed at the MP2/6‐311G** level. It has been found that studied phenylselanylalkenes adopt mainly skewed s‐cis conformation with the noticeable out‐of‐plane deviations of the phenylselanyl and phenyl groups. Copyright © 2011 John Wiley & Sons, Ltd.