An ab initio study of 15N-11B spin-spin coupling constants for borazine and selected derivatives

Ab initio equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) calculations have been performed to investigate substituent effects on coupling constants for borazine and selected substituted borazines. For molecules in which F atoms are not bonded to adjacent atoms in the ring, F substitution increases the one-bond (11)B-(15)N coupling constants involving the atom at which substitution occurs but leaves the remaining one-bond B-N coupling constants essentially unchanged. For these molecules, the magnitudes of one-bond B-N coupling constants are only slightly dependent on the number of F atoms present. Fluorine substitution at adjacent B and N atoms in the borazine ring further increases the one-bond B-N coupling constant involving the substituted atoms and has the same effect on the other one-bond coupling constants as observed for corresponding molecules in which substitution occurs at alternate sites. In contrast to the effect of F substitution, substitution of Li at either N or B decreases one-bond B-N coupling constants relative to borazine. The effects of F and Li substitution on one-bond B-N coupling constants for borazine are similar to F and Li substitution effects on (13)C-(13)C coupling constants for benzene.     

Selective population transfer in 15N and 13C NMR: Signs of 15N?H and 15N?13C coupling constants in secondary amide and iminium salts

The selective population transfer method has been applied to the study of a secondary amide and of the corresponding iminium salt. Important signal-to-noise enhancements were accessible in both fully coupled and proton decoupled ¹⁵N and ¹³C spectra. Moreover, the resolving power of the method was exploited for the accurate determination of long range ¹⁵N¹H coupling constants. Experiments in which the selective inversion of transitions pertaining to the ¹⁵N satellite spectrum of multiplets which themselves constitute the ¹³C satellite spectrum of the main proton resonances could be carried out. The influence of a change from the amide to the iminium structure on the magnitudes and the signs of various ¹⁵N¹H and ¹⁵N¹³C coupling constants is discussed.     

Rotational spectrum and carbon-13 hyperfine structure of the C3H, C5H, C6H, and C7H radicals

By means of Fourier transform microwave spectroscopy of a supersonic molecular beam, we have detected the singly substituted carbon-13 isotopic species of C(5)H, C(6)H, and C(7)H. Hyperfine structure in the rotational transitions of the lowest-energy fine structure component ((2)Pi(12) for C(5)H and C(7)H, and (2)Pi(32) for C(6)H) of each species was measured between 6 and 22 GHz, and precise rotational, centrifugal distortion, Lambda-doubling, and (13)C hyperfine coupling constants were determined. In addition, resolved hyperfine structure in the lowest rotational transition (J = 32-->12) of the three (13)C isotopic species of C(3)H was measured by the same technique. By combining the centimeter-wave measurements here with previous millimeter-wave data, a complete set of (13)C hyperfine coupling constants were derived to high precision for each isotopic species. Experimental structures (r(0)) have been determined for C(5)H and the two longer carbon-chain radicals, and these are found to be in good agreement with the predictions of high-level coupled-cluster calculations. C(3)H, C(5)H, and C(7)H exhibit a clear alternation in the magnitude and sign of the (13)C hyperfine coupling constants along the carbon-chain backbone. Because the electron spin density is nominally zero at the central carbon atom of C(3)H, C(5)H, and C(7)H, and at alternating sets of carbon atoms of C(5)H and C(7)H, owing to spin polarization, almost all of the (13)C coupling constants at these atoms are small in magnitude and negative in sign. Spin-polarization effects are known to be important for the Fermi-contact (b(F)) term, but prior to the work here they have generally been neglected for the hyperfine terms a, c, and d.     

Self-consistent Perturbation Theory of 13C magnetic resonance parameters in pyridines

The ¹³C chemical shifts for pyridine and 22 of its monosubstituted derivatives, the ¹³C? ¹⁹F couplings for fluoropyridines and the ¹³C? ¹⁵N couplings for pyridine, the pyridinium cation and pyridine-N-oxide have been calculated using the SCF-INDO Finite Perturbation Theory. Experimental ¹³C chemical shifts show only modest correlation with calculated shieldings; trends and magnitudes are, however, reasonably reproduced in some cases. Theory yields a correct account of the magnitudes, signs and trends for the various couplings except for ²J(CF). Addition of an empirical correction of + 33.5 Hz to the Fermi contact term leads also to excellent reproduction of this coupling.     

Hydroacridines: part 29. 15N NMR chemical shifts of 9-substituted 1,2,3,4,5,6,7,8-octahydroacridines and their N-oxides-Taft, Swain-Lupton, and other types of linear correlations

The (15)N NMR chemical shifts of 1,2,3,4,5,6,7,8-octahydroacridine, 12 of its 9-substituted derivatives, and of the corresponding N-oxides were measured and examined in terms of the 9-substituent effects and the effects of N-oxidation. For the 9-substituent effects, good linear correlations were found with the Taft and Swain-Lupton substituent constants, for both octahydroacridines and their N-oxides. The (15)N chemical shifts of both octahydroacridines and their N-oxides also correlate well, linearly with the (13)C chemical shifts of the para-carbons in analogously substituted benzene derivatives.Within the studied compounds, the magnitudes of the N-oxidation effects range from - 16.4 to - 27.4 ppm (shielding), and also correlate linearly with the Taft and Swain-Lupton substituent constants, as well as with the bond orders of the N(+)-O(-) bonds in the corresponding N-oxides. Furthermore, a very good linear correlation is found between the (15)N chemical shifts of octahydroacridines and those of the corresponding N-oxides. From the (15)N chemical shifts data, the Taft and Swain-Lupton substituent constants for the diacetylamino group (-NAc(2)) were evaluated in the present paper, as follows: sigma(R) = 0.07 and sigma(I) = 0.15; R = 0.08 and F= 0.20.     

13C, 13C coupling constants in phenyl substituted ethylene,naphthalene, phenanthrene and cyclopentadienone. Dependence on dihedral angles. Determination of signs by the symmetrical double labelling (SDL) method. IV

Carbon-13, carbon-13 coupling constants and carbon-13 chemical shifts have been measured in a series of phenyl substituted ethylenes and aromatics all doubly labelled with ¹³C at the olefinic positions (α,β-) or at neighbouring aromatic positions, tetraphenylcyclopentadienone labelled at the 3,4-positions, and dichlorodiphenylmethane labelled at the α-carbon. Signs of coupling constants were determined by the symmetrical double labelling (SDL) method. Coupling constants over as many as five bonds are reported. Two-bond couplings between carbons in the aromatic skeleton belong to different classes according to the nature of the coupling path. The magnitudes of three-bond coupling constants between such carbons correlate linearly with π-bond orders and a separation of the δ- and π-contributions is evident. The three-bond couplings between the 2-position in a phenyl substituent and the olefinic β-position or a corresponding aromatic position depend on the out-of-plane twist of the phenyl ring and may lead to information about the twist angle. Contrary to findings with aromatic carbonyl compounds two- and three-bond couplings to the α-carbon in the present compounds are fairly constant. The reported data suggest that the signs of coupling constants over more than two bonds alternate in aromatic systems. Carbon-13, carbon-13 coupling constants in naphthalene have been calculated by the INDO-SOS method.     

13C?13C coupling constants and substituent effects on 13C chemical shifts in 13C labelled pyrene and pyrene derivatives

Long range inter-ring ¹³C? ¹³C couplings are found to be effective in the title compounds, and the magnitudes of coupling constants and of substituent effects on ¹³C chemical shifts, as well as the signs of the latter, alternate with respect to the number of connecting bonds.     

1H, 1 3C,and 1 5N Chemical shifts and 1H-1 5N and 1 3C-1 5N heteronuclear spin-spin coupling constants in the NMR spectra of 5-substituted furfural oximes

The ¹H, ¹³C, and ¹⁵N NMR spectra of ¹⁵N-enriched 5-substituted furfural oximes were investigated. It was shown that the chemical shifts of the ring atoms and the oxime group correlate satisfactorily with the F and R substituent constants, whereas their sensitivity to the effect of the substituents is lower than in monosubstituted furan derivatives. The constants of spin-spin coupling between the ring protons and the oxime group were determined. An analysis of the ¹H-¹H spin-spin coupling constants (SSCC) on the basis of their stereospecificity indicates that the E isomers have primarily an s-trans conformation in polar dimethyl sulfoxide, whereas the Z isomers, on the other hand, have an s-cis conformation. The signs of the direct and geminal ¹³C-¹⁵N SSCC were determined for 5-trimethylsilylfurfural oxime.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1172–1177, September, 1985.The authors thank N. O. Saldabol, L. M. Ignatovich, and N. P. Erchak for providing us with the investigated compounds.     

Relative signs of 29Si-13C couplings

Two pulse sequences applicable to the determination of relative signs of coupling constants, gHSQC-RELAY(P) and gHSQC-RELAY(D), were developed and tested. These sequences are suitable for determination of relative signs of long-range coupling constants (<2 Hz) between two heteronuclei of low abundance (such as (29)Si and (13)C), and are applicable even to cases in which one of the heteronuclei ((29)Si) does not exhibit coupling with some of the detected protons ((1)H). The two sequences differ in the manner in which they suppress undesirable homonuclear coherence transfers. Each of the sequences can be combined with an isotope filter for better suppression of the centerlines arising from more abundant NMR-inactive isotopes. The sequences were tested on ethoxytrimethylsilane and (E)-(buta-1,3-dienyloxy)trimethylsilane, and we conclude that (2)J((29)Si-O-(13)C) is positive while (3)J((29)Si-O-C-(13)C) is negative in both compounds.     

High resolution NMR spectroscopy of heteroaromatic cations. I. 13C?1H coupling constants in the pyridinium cation

High-resolution ¹H? {¹⁴N} and proton-coupled natural-abundance ¹³C? {¹⁴N} double resonance spectra have been recorded for pyridinium tetrafluoroborate dissolved in CD₃CN. Iterative analysis of these spectra has provided the accurate values and relative signs of all possible long-range ¹³C—¹H coupling constants. These are compared with the respective values in pyridine and pyridine-N-oxide and discussed in terms of the relationship with the electronegativity of the N-substituent. Experimental conditions allowing the observation of well-resolved proton-coupled ¹³C NMR spectra of charged heteroaromatics are also presented.     

1H and 13C NMR studies on 1,3,2-dioxarsolanes

The ¹H and ¹³C NMR spectra of a series of 1,3,2-dioxarsolanes have been obtained at 2.1 T and some at 9.4 T. The chemical shifts and spin-spin coupling constants have been obtained from complete spectral analyses of the ¹H and proton-coupled ¹³C spectra. The spectral data are interpreted on the basis of two rapidly interconverting half-chair conformers with a pseudoaxial substituent at arsenic. Unique assignment of syn/anti or cis/trans geometries have been made from ¹H or ¹³C NMR spectroscopy alone. The syn and trans isomers of the 4-methyl- and 4,5-dimethyl-1,3,2-dioxarsolanes, respectively, appear to be conformationally biased towards the forms with pseudoequatorial methyl groups. The general trends in the geminal and vicinal ¹H? ¹H and ¹³C? ¹H coupling constants are interpreted in terms of stereospecific, electronegativity and lone-pair effects of the oxygen heteroatoms and conformational factors. The NMR data on the 1,3,2-dioxarsolanes are discussed with reference to related 1,3-dithoxa- and 1,3-dithia- five-membered rings with As, P, S or C at the 2-position.     

The NMR spectra of some fluorinated pyridine derivatives

The ¹H and ¹⁹F spectra of a variety of mono- and di- fluorinated pyridines are examined, and compared with the corresponding spectra of the pyridinium ions. The magnitudes and signs of the ¹H? ¹⁹F coupling constants are in general in accord with those observed for the corresponding ¹H? ¹H couplings, with an exaggerated range. Large changes in the NMR parameters are observed on protonation of the nitrogen, ³J(H? F) changing sign in some of the α-fluoropyridine derivatives.     

15N-1H and 15N-13C couplings in 15N-enriched dihydroxamic acids

(15)N-enriched dihydroxamic acids (HONHCO(CH(2))(n)CONHOH, n = 0, 1, and 2) were prepared and their spectra NMR ((1)H, (13)C, (15)N) recorded in dimethyl sulfoxide (DMSO) solutions with the aim of determining (15)N coupling constants ((15)N-(1)H and (15)N-(13)C). The results supplement chemical shifts published earlier and yield additional support to the structural conclusions derived from other NMR parameters. Notably, no trace of hydroximic structures could be found in the (15)N NMR spectra of these acids. The values of (15)N-(13)C coupling constants backed by theoretical calculations support the assignments made earlier for all of the major conformers and for the minor conformer of succinohydroxamic acid. The enrichment revealed that the minor component of malonodihydroxamic acid solution previously considered to be the ZE conformer is in fact the monohydroxamic acid (HOOC-CH(2)-CO-NH-OH).     

Experimental and quantum-chemical studies of 1H, 13C and 15N NMR coordination shifts in Pd(II) and Pt(II) chloride complexes with quinoline, isoquinoline, and 2,2'-biquinoline

1H, 13C, and 15N NMR studies of platinide(II) (M=Pd, Pt) chloride complexes with quinolines (L=quinoline-quin, or isoquinoline-isoquin; LL=2,2'-biquinoline-bquin), having the general formulae trans-/cis-[ML2Cl2] and [M(LL)Cl2], were performed and the respective chemical shifts (delta1H, delta13C, delta15N) reported. 1H coordination shifts of various signs and magnitudes (Delta1Hcoord=delta1Hcomplex-delta1Hligand) are discussed in relation to the changes of diamagnetic contribution to the relevant 1H shielding constants. The comparison to the literature data for similar complexes containing auxiliary ligands other than chlorides exhibited a large dependence of delta1H parameters on electron density variations and ring-current effects (inductive and anisotropic phenomena). The influence of deviations from planarity, concerning either MN2Cl2 chromophores or azine ring systems, revealed by the known X-ray structures of [Pd(bquin)Cl2] and [Pt(bquin)Cl2], is discussed in respect to 1H NMR spectra. 15N coordination shifts (Delta15Ncoord=delta15Ncomplex-delta15Nligand) of ca. 78-100 ppm (to lower frequency) are attributed mainly to the decrease of the absolute value of paramagnetic contribution in the relevant 15N shielding constants, this phenomenon being noticeably dependent on the type of a platinide metal and coordination sphere geometry. The absolute magnitude of Delta15Ncoord parameter increased by ca 15 ppm upon Pd(II)-->Pt(II) replacement but decreased by ca. 15 ppm following trans-->cis transition. Experimental 1H, 13C, 15N NMR chemical shifts are compared to those quantum-chemically calculated by B3LYP/LanL2DZ+6-31G**//B3LYP/LanL2DZ+6-31G*, both in vacuo and in CHCl3 or DMF solution.     

13C/15N distance determination by CPMAS NMR in uniformly 13C labeled molecules

The REDOR and CPMAS techniques are applied for measuring 13C-15N dipolar coupling constants in glycine. It is shown that the selective CP or SPECIFIC CP technique removes the coherent evolution of the spin system under homonuclear 13C-13C J couplings. While the large coupling constant (approximately 900 Hz) is readily determined because of the presence of large oscillations in the CPMAS dynamics, their absence precludes the measurement of the small coupling constant (approximately 200 Hz). The experimental results and numerical simulations demonstrate that the determination of 13C-15N coupling constants of medium size (<1 kHz) by the CPMAS technique is mainly limited by the strength of the 1H decoupling field and the size of the 13C and 15N chemical shift anisotropies.     

Etude en RMN 13C de Spiropyrannes Hétérocycliques

A ¹³C n.m.r. study of different heterocyclic spiropyrans has been carried out. We have attempted to describe the specific influence of the heteroatoms on the chemical shift of the neighbouring atoms. Carbon-13 chemical shifts and coupling constants have been also obtained for compounds similar to both parts of the spiropyran molecule: the heterocycle and the benzopyran.     

Multinuclear NMR Studies of the Substitlent Effects in N-Phenyl-P,P,P-Triarylphospha-λ5-Azenes,Triaryl-Phosphines and Triarylphosphine Oxides

Abstract

A series of N-phenyl-P,P,P-triarylphospha-λ⁵-azenes (1) as well as their ^l5N labeled analogs was synthesized. The ¹³C, ³¹P, and ¹⁵N NMR spectra of this series and those of two other series of related compounds, namely triarylphosphines (2) and triarylphosphine oxides (3), were measured and are reported. Many satisfactory correlations using the mono-substituent parameter (MSP) and the Taft dual-substituent parameter (DSP) treatments with the ¹³C substituent chemical shifts (SCS), ³¹P SCS, ¹⁵N SCS and the one bond P-N, P-C and C-N coupling constants were observed and will be discussed. Thus, for example, the ³¹P and ¹⁵N chemical shifts in 1 correlated with [sgrave]^?with negative slopes while the ³¹P chemical shifts in 3 correlated with those in 1 with a slope of 2.0. The ¹³C chemical shifts in 1 correlated excellently with the corresponding ones in 3 with slopes very close to unity. The substituent effects on the chemical shifts of the various nuclei were shown to be mainly due to changes in the charge distribution on those nuclei. In 1 the one bond P-N and P-C coupling constants correlated with [sgrave]_p and [sgrave]_R respectively. The one bond P-C coupling constants of 1 correlated quite well with those of 3 with a slope of 0.93 while the corresponding correlation of 1 with 2 was quite poor. Taft DSP treatment of ¹J_PCin 1 and 3 were quite similar, ρI and ρR were both negative and ρR was much larger than ρI. Series 2 showed behavior which was different from that shown by 1 and 3 but similar to that shown by other systems with a lone electron pair on the atom bound to the phenyl ring. The substituent effects on the one bond P-N, P-C and C-N coupling constants will be discussed in terms of bonding and hybridization changes between the directly bonded nuclei.     

29Si-13C spin-spin couplings over an Si-O-Csp3 link

(29)Si-(13)C spin-spin couplings over one, two, and three bonds as well as other NMR parameters [delta((29)Si), delta((13)C), delta((1)H), (1)J((13)C-(1)H), and (2)J((29)Si-C-(1)H)] were calculated and measured for a series of trimethylsilylated alcohols of the types Me(3)Si-O-(CH(2))(n)CH(3) and Me(3)Si-O-CH(3-n)R(n)(n = 0-3; R = Me, Ph, or Vi). The signs of the coupling constants determined for selected compounds can likely be extended to all such compounds, as supported by theoretical calculations. Similar to couplings between other pairs of nuclei, the 2-bond and 3-bond (29)Si-O-(13)C couplings are of opposite signs ((2)J > 0 and (3)J < 0), and their relative magnitudes depend on the extent of branching at the alpha-carbon.     

1H and 13C NMR studies of 7-azaindole and related compounds

The ¹H and ¹³C chemical shifts, proton-proton coupling constants, and one-bond carbon-hydrogen coupling constants have been obtained for 7-azaindole, 1-methyl-7-azaindole, their corresponding methyl iodide salts, and the related compound 7-methyl-7H-pyrrolo [2,3-b]pyridine. are different from those of either 7-azaindole or 1-methyl-7-azaindole.     

Probing the proton-transfer coordinate of complexes with F--H...P hydrogen bonds using one- and two-bond spin-spin coupling constants

Scalar coupling constants have been computed using the EOM-CCSD method for equilibrium structures of complexes stabilized by F--H...P hydrogen bonds, as well as structures along the proton-transfer coordinates of these complexes. Variations in the signs and absolute values of (1)J(F--H), (1h)J(H--P) and (2h)J(F--P) have been analyzed and interpreted in terms of changing hydrogen bond type. Of the three phosphorus bases (phosphine, trimethylphosphine and phosphinine) investigated in this study, trimethylphosphine forms the strongest complex with FH, and has the largest two-bond F--P coupling constant. Among the relatively simple phosphorus bases, it would appear to be a leading candidate for experimental NMR study. Similarities and differences are noted between the corresponding coupling constants (J) and the reduced coupling constants (K) across F--H...P and F--H...N hydrogen bonds.