Stereochemistry of the tin—carbon bond: I. Synthesis and characterization by 13C and 119Sn NMR of a series of exo- and endo-2-triorganostannylnorbornanes

A series of endo- and exo-2-triorganostannylnorbornanes have been synthesized by various methods, some of them leading to pure stereoisomers. The 2-triorganostannylnorbornanes have been characterized by their ¹³C and ¹¹⁹Sn NMR spectra.     

Détermination par RMN 1H et 13C des Couplages J(CH) et J(CC) dans des Monomères Precurseurs de Lignine: Vanilline,Férulate d'Ethyle et Alcool Coniférylique Sélectivement Enrichis en 2H et 13C

Some monomer model compounds of lignin have been selectively ²H and ¹³C labelled: vanillin, ethyl ferulate, coniferyl alcohol and ethyl hydrogen malonate. Deuterium isotope effects on the ¹³C chemical shifts in [formyl-²H]vanillin, [5-²H]vanillin and [α,α,5-²H₃]coniferyl alcohol made the unambiguous assignment of the aromatic ¹³C signals possible. Absolute ^1,2,3J(CC) values have been determined on ¹³C spectra of [formyl-¹³C]vanillin, and of ethyl ferulate and coniferyl alcohol in which the vinylic C-γ and C-β carbons were ¹³C enriched. It has been possible to measure ⁴J(C?O, C-4) in vanillin and ⁴J(C-γ, C-4) in ethyl ferulate. The determination of ^1,2,3,4J (CH) absolute values was done by means of gated decoupled ¹³C spectra of the non-labelled compounds. When second order effects made the use of this technique impossible we determined certain J(CH) values and their signs either by analysing the ¹H NMR spectra of ¹³C labelled coniferyl alcohol [²J(C-β, H-γ), ²J(C-β, H-α), ²J(C-γ, H-β), ³J(C-γ, H-α)] or by a double irradiation experiment on the 250 MHz ¹H NMR spectrum of ethyl [β-¹³C] ferulate [for ²J(C-β, H-γ)].     

Proton-coupled 13C NMR and {14N}—1H-INDOR of highly-substituted 6-membered heterocycles. I—trisubstituted pyridones and isomeric aminopyrones; tetrasubstituted pyridines

The structural elucidation by NMR spectroscopy of trisubstituted α-pyridones and the isomeric 2-amino-γ-pyrones as well as their internal and external pyrylium salts is described. The most useful parameter for the differentiation between α-pyridones and isomeric γ-pyrones is the geminal coupling constant ²J(C-6, H-5) which changes from ～2.5 Hz to ～7 Hz whenever the cyclic amide group is replaced by an oxa-function; this applies to both the γ-pyrones and their pyrylium salts. The value of J(C-6, H-5) in the pyridones resembles that of the analogous coupling in N-vinylacetamide, whose sign determination by the selective population inversion (SPI) technique is reported. The ¹³C chemical shifts of seven pyridones, pyrones and pyrylium salts are reported and their structural correlations are discussed. Quick structural assignments in these classes of compounds may also be performed by evaluating the ¹⁴N chemical shifts, which often are accessible by the {¹⁴N}—¹H-INDOR technique. The proton coupled ¹³C NMR spectra of two tetrasubstituted pyridines are also reported, and empirical correlations between long range C? H coupling constants and substituent electronegativity are discussed.     

A Photoelectron-spectroscopic investigation of the Homoconjugative Interaction between π- and Walsh-Orbitals in endo- and exo-Cyclopropano-norbornene

Photoelectron spectra of endo- and exo-cyclopropano-norbornene ( = endo- and exo-tricyclo[3.2.1.0^2.4]octa-6-ene) show that a significant homoconjugation exists between the π-orbital of the double bond and the symmetric Walsh-es-orbital of the cyclopropane ring in the exo-isomer, whereas the interaction is negligeable in the endo-derivative.     

Dérivés Alléniques de l'Étain,du Plomb et du Mercure. Signes Relatifs des Constantes de Couplage Métal-Proton á Travers Deux et Quatre Liaisons

Satellites corresponding to metal-proton coupling constants through two and four bonds are observed in PMR spectra of Pb, Sn and Hg allenic derivatives. The relative signs of these coupling constants are deduced from analysis of the satellite spectra: ²J(X? H) and ⁴J(X? H) are of opposite signs for X = ²⁰⁷Pb, ¹¹⁹Sn, ¹¹⁷Sn and of same sign for X = ¹⁹⁹Hg. Probable absolute signs of reduced coupling constants are discussed in relation to published data: ²K(X? C? H) is probably positive for X = ²⁰⁷Pb, ¹¹⁹Sn, ¹¹⁷Sn and ¹⁹⁹Hg. ⁴K(X? C?C?C? H) is probably negative for X = ²⁰⁷Pb, ¹¹⁹Sn, ¹¹⁷Sn and positive for X = ¹⁹⁹Hg.     

Diorganotin complexes of carboxylates: synthesis and characterization

Diorganotin complexes of monoisopropyl and monomethyl nadiate, succinate, and phthalate were synthesized and characterized by elemental analysis, FT-IR, ¹H NMR, ¹³C NMR, and ¹¹⁹Sn NMR spectroscopic techniques. The spectroscopic investigation demonstrated that carboxylate is bidentate in the diorganotin complexes. On the basis of ¹ J(¹¹⁹Sn–¹³C) and ² J(¹¹⁹Sn–¹H) values, C–Sn–C bond angles were also calculated. The newly synthesized complexes were also screened for their antibacterial activities against Gram-positive and Gram-negative pathogenic strains of bacteria.     

13C and 119Sn NMR spectra of Di-n-butyltin(IV) compounds

The ¹³C and ¹¹⁹Sn NMR spectra of a set of di-n-butyltin(IV) compounds and their complexes in coordinating and non-coordinating solvents have been studied. The results have shown that it is possible to describe semiquantitatively the shape of coordination polyhedra of these compounds from analysis of their δ(¹¹⁹Sn) and ¹J(¹¹⁹Sn-¹³C) parameters. The values of δ(¹¹⁹Sn) define the regions with different coordination numbers of the central tin atom, so that four-coordinate compounds have δ(¹¹⁹Sn) ranging from about + 200 to −60 ppm, five-coordinate compounds, −90 to −190 ppm, and six-coordinate compounds, −210 to −400 ppm. The values of ¹J(¹¹⁹Sn-¹³C) were used for the calculation of the CSnC angle in the coordination polyhedron of individual compounds.     

Signs of proximate 31P, 19F and 19F, 19F spin–spin coupling constants in 2-trifluoromethylphenyldifluorophosphine

In 2-trifluoromethylphenyldifluorophosphine the proximate couplings ⁴J(¹⁹F³¹P) and ⁵J(¹⁹F¹⁹F) are + 68.3 and + 8.3 Hz, respectively. ¹J(¹³C³¹P) is ?57.0 Hz, ²J(¹³C-1, ¹⁰F) is + 9.9 Hz and ²J(¹³C-6, ¹³C-6, ³¹P) is + 10.1 Hz. The trifluoromethyl substituent induces substantial changes in some coupling constants, particularly those between the ³¹P and ring ¹³C nuclei.     

Carbon-13 n.m.r. studies. 65—13C spectra of some tricyclo[3.2.1.02,4]octane derivatives

The ¹³C n.m.r. spectra of 18 derivatives of the tricyclo[3.2.1.0^2,4]octanes have been determined. This series includes methyl, hydroxyl and oxo substituted examples to compare the effects of these substituents on the skeletal carbon shieldings with those observed for the corresponding norbornanes and bicyclo[3.2.1]octanes. In general, the trends are similar and the perturbations associated with closely neighboring groups follow a consistent pattern. The shielding data for the exo–exo and exo–endo isomers of tetracyclo[3.3.1.0^2,40^6,8]nonane are also reported.     

13C and 119Sn NMR spectra of some tribenzyltin(IV) compounds

The ¹³C and ¹¹⁹Sn NMR spectra of some tribenzyltin(IV) compounds and their complexes in coordinating and non-coordinating solvents have been studied. The δ(¹¹⁹Sn) chemical shifts and coupling constants ¹J(¹¹⁹Sn, ¹³C) clearly depend on the coordination number of the central tin atom and the geometry of its coordination polyhedra. Approximate ranges of the characteristic values of both the NMR parameters were determined for various configurational types of tribenzyltin compound. The ¹³C and ¹¹⁹Sn NMR parameters found are indicative of a distinct interaction between the polarized σ(SnC) bond and adjacent π-electron system of the aromatic ring(s).     

Reactions of p-Nitrophenyloxirane with Amines Containing Fragments with Bicyclic Skeleton

Reactions of p-nitrophenyloxirane with amines containing fragments with bicyclic skeleton of norbornene, norbornane, epoxynorbornane (stereoisomeric exo- and endo-5-aminomethylbicyclo[2.2.1]hept-2-enes, N-benzyl-endo-5-aminomethylbicyclo[2.2.1]hept-2-ene, endo-5-(2-aminoethyl)bicyclo[2.2.1]hept-2-ene, stereoisomeric exo- and endo-2-aminomethylbicyclo[2.2.1]heptanes, 2-(1-aminoethyl)bicyclo[2.2.1]heptane, exo-5-aminomethyl-exo-2,3-epoxybicyclo[2.2.1]heptane) were investigated. The aminolysis of p-nitrophenyloxirane occurred regioselectively according to Krasusky rule as was proved by ¹H and ¹³C NMR data. As shown by ¹H and ¹³C NMR spectroscopy the oxyalkylation product obtained from N-benzyl-endo-5-aminomethylbicyclo[2.2.1]hept-2-ene was composed of two diastereomers originating from the presence of a chiral nitrogen atom in the rear part of the rigid bicyclic skeleton. New products of amino groups transformation in the molecules of hydroxyamines were obtained by reaction with p-methylbenzoyl chloride and p-nitrophenylsulfonyl chloride. Regioselectivity of the attack of electrophilic reagents on the nitrogen in the hydroxyamines was confirmed by IR and ¹H NMR spectra of the products. The data on pharmacological activity tests of N-2-hydroxyethyl(p-nitrophenyl)-5-aminomethylbicyclo[2.2.1]hept-2-ene are reported.     

Three‐centre Rh?H?Sn bonds: an NMR study of the effects of varying the electron density on rhodium

The complexes [Rh(X)(H)(SnPh₃)(PPh₃)(L)] (X = NCBPh₃ (a), N(CN)₂ (b), NCS (c), NCO (d), N₃ (e); L = 1‐methylimidazole) ( 1 ) show systematic changes in δ(¹¹⁹Sn), δ(¹⁰³Rh), J(¹¹⁹Sn–¹H) and J(¹¹⁹Sn–¹⁰³Rh) that are related to the electron‐donating properties of X. As X becomes more electron‐rich, δ(¹⁰³Rh), J(¹¹⁹Sn–¹H) and J(¹¹⁹Sn–¹⁰³Rh) increase and δ¹¹⁹Sn) decreases. The related complexes trans‐[Rh(X)(H)(SnPh₃)(PPh₃)₂(L)] (X = N(CN)₂, NCO; L = 4‐carboxymethylpyridine (x), pyridine (y) and 4‐dimethylaminopyridine (z)) ( 2 ), show a continuation of the trends in δ(¹¹⁹Sn) and J(¹¹⁹Sn–¹H), but not δ(¹⁰³Rh) or J(¹¹⁹Sn–¹⁰³Rh). Data for 1 and 2 show that within certain limits of type of ligand varied (X = N‐donor, L = a pyridine) and coordination geometry, the response of δ(¹¹⁹Sn) and J(¹¹⁹Sn–¹H) to changes in electron density on rhodium is largely independent of the means by which the change is effected.Copyright © 2001 John Wiley & Sons, Ltd.     

Solution conformation and dynamics of L-6-methylperhydroimidazo[1,5-c]thiazole-5,7-dione (γ-thiaprolinehydantoin). A 1H and 13C NMR study

The solution conformation of L-6-methylperhydroimidazo[1,5-c]thiazole-5,7-dione (γ-thiaprolinehydantoin) has been determined from an extensive ¹H and ¹³C NMR study, allowing the extraction of vicinal inter-proton and carbon-hydrogen coupling constants. The major conformation of the thiazolidine ring is an envelope with C-δ as the flap exo (δ^?). In solution the preferred solid state (twist) conformer with C-α exo and C-β endo (_α^βT) is only a minor contributor. ¹³C spin–lattice relaxation data reveal the flexibility of the thiazolidine ring.     

13C nuclear magnetic resonance spectroscopy of selected adenine nucleosides: Structural correlation and conformation about the glycosidic bond

Structural correlations have been carried out from ¹³C chemical shifts (δ) and by analysis of ¹J(CH) coupling constants, and the conformation about the glycosidic bond has been studied by means of the ³J(CH) vicinal coupling constants between C-8 and H-1′ of some adenine nucleosides such as adenosine (Ado), N(7)-β-D-ribofuranosyladenine (N(7)-Ado), N(9)- and N(7)-β-D-xylofuranosyladenine (N(9)-xylAde and N(7)-xylAde), N(9)-(3-chloro-3-deoxy-β-D-xylofuranosyl)adenine (3′-Cl-xylAde) and N(9)-(2-chloro-2-deoxy-β-D-arabinofuranosyl)adenine (2′-Cl-araAde). The analysis of the influence on δ¹³C of the nature and configuration of the substituent in the carbohydrate fragment of the molecule has revealed two types of effects, namely, 1,2-cis and 1,2-trans. This approach, as well as the ³J(CH) values and the analysis of the C-3′-endo?C-2′-endo equilibrium of the carbohydrate fragment of nucleosides, and circular dichroism (CD) data, provides important information on the conformation about the glycosidic bond. The magnitudes of ³J(C-4, H) are indicative of the position of attachment of the carbohydrate fragment to the heterocyclic base.     

La résonance magnétique du 77Se dans des composés organiques

⁷⁷Se n.m.r. spectra of twenty-six organoselenium compounds, including some with an endocyclic selenium atom, have been recorded. Our measurements complete the scale of chemical shifts previously established by McFarlane. It seems difficult to define a range of chemical shifts which is characteristic of the valency state of selenium or of its endo- or exocyclic position. Some results are discussed qualitatively. In the case of selenolo[2,3-b]thiophene, evidence has been obtained for a ⁴J[Se, H] coupling across the sulphur atom.     

Investigation of the exo and endo isomers of dioxolane-type benzylidene derivatives of carbohydrates by 13C NMR spectroscopy

The absolute configurations of nine 2,3-O-benzylidene-α-L-rhamno- and α-D-mannopyranoside diasteteomeric pairs were determined and the ¹³C NMR spectra of further thirteen α-L-rhamno- and α-D-mannopyranosides, having various substituents, were completely assigned.Four ¹³C shifts were found suitable for the determination of the absolute configuration of the dioxolane skeleton. (1) The chemical shift of the acetal carbon in the endo isomers is between 103.9 and 104.7 ppm whereas for the exo isomers this region extends from 102.8 to 103.4 ppm; (2) The formation of the dioxolane ring causes a deshielding effect for the bridgehead carbons, in the exo isomers this effect is more pronounced for C-3 whereas in the endo isomers for C-2. For C-4, shielding effect was found in the exo isomers and deshielding effect in the endo ones; (3) The chemical shift of the quaternary carbon of the phenyl group is greater in the exo isomers than in the endo ones; (4) The difference between the shift of the acetal carbon and that of the quaternary carbon of the phenyl group in the exo isomers is greater than 35.4 ppm, in the endo isomers is less than 33.7 ppm.     

195Pt, 119Sn and 31P NMR studies of alkyl,aryl and acyl trichlorostannate complexes of platinum(II). The crystal structure of trans-[Pt(SnCl3)(COC6H5)(PEt3)2]

¹⁹⁵Pt, ¹¹⁹Sn and ³¹P NMR characteristics of the complexes trans-[Pt(SnCl₃)(carbon ligand)(PEt₃)₂] (1a-1e) are reported, (carbon ligand = CH₃ (1a), CH₂Ph (1b), COPh (1c), C₆Cl₅ (1d), C₆Cl₄Y (e); Y = meta- and para-NO₂, CF₃, Br, H, CH₃, OCH₃, or Pt(SnCl₃)(PEt₃)₂. The values of ¹J(¹⁹⁵Pt, ¹¹⁹Sn) vary from 2376 to 11895 Hz with the COPh ligand having the smallest and the C₆Cl₅ ligand the largest value, making a total range for this coupling constant, when the dimer syn-trans-[PtCl(SnCl₃)(PEt₃)]₂ is included, of ca. 33000 Hz. In the meta- and para-substituted phenyl complexes ¹J(¹⁹⁵Pt, ¹¹⁹Sn) (a) is greater for electron-withdrawing substituents, (b) varies more for the meta-substituted derivatives (5634 to 7906 Hz) than for the para analogues (6088 to 7644 Hz) and (c) has the lowest values when the Pt(SnCl₃)(PEt₃)₂ group is the meta- or para-substituent. The direction of the change in ¹J(¹⁹⁵Pt, ¹¹⁹Sn) is opposite to that found for ¹J(¹⁹⁵Pt, ¹¹⁹P). For the aryl complexes linear correlations are observed between δ(¹¹⁹Sn), ¹J(¹⁹⁵Pt, ¹¹⁹Sn), ¹J(¹⁹⁵Pt, ³¹P), ¹J(¹¹⁹Sn, ³¹P) and the Hammett substituent constant σⁿ. δ(¹¹⁹Sn) and ¹J(¹⁹⁵Pt, ¹¹⁹Sn) are related linearly to v(Pt-H) in the complexes trans-[PtH(C₆H₄Y)(PEt₃)₂]; δ(¹¹⁹Sn) and δ(¹H) (hydride) are also linearly related. Based on ¹J(¹⁹⁵Pt, ¹¹⁹Sn), the acyl ligand is suggested to have a very large NMR trans influence. The differences in the NMR parameters for (1a-e) are rationalized in terms of differing σ- and π-bonding abilities of the carbon ligands.The structure of 1c has been determined by crystallographic methods. The complex has a slightly distorted square planar geometry with trans-PEt₃ ligands. Relevant bond lengths (Å) and bond angles (°) are: PtSn, 2.634(1), PtP, 2.324(4) and 2.329(4), PtC, 2.05(1); PPtP, 170.7(6), SnPtC, 173.0(3), SnPtP, 92.1(1), 91.7(1), PPtC, 88.8(4) and 88.3(4). The PtSn bond separation is the longest yet observed for square-planar platinum trichlorostannate complexes, and would be consistent with a large crystallographic trans influence of the benzoyl ligand. The PtSn bond separation is shown to correlate with ¹J(¹⁹⁵Pt, ¹¹⁹Sn).     

Synthesis, 119Sn, 13C and 195Pt NMR studies of five-coordinate rhodium(I), iridium(I) and platinum(II) complexes containing three trichlorostannate ligands

The synthesis and ¹¹⁹Sn NMR characteristics of new five-coordinate tris(trichlorostannato) complexes of Rh^I, Ir^I and Pt^II are reported. The Rh^I and Ir^I complexes are complex dianions of the form (PPN)₂[M(SnCl₃)₃L₂] where L can be CO, CN (cyclohexyl) or L₂, a diolefin such as 1,5-COD or NBD (norbornadiene). The anionic platinum complexes (PPN)[Pt(SnCl₃)₃L₂] contain similar L ligands. A number of neutral monotrichlorostannato complexes of type [M(SnCl₃)L₄] including [Ir(SnCl₃)(NBD)(1,5-COD)] have been prepared and characterized. Their δ(¹¹⁹Sn), δ(¹³C), δ(¹⁹⁵Pt) as well as ¹J(¹⁰³Rh, ¹¹⁹Sn), ¹J(¹⁹⁵Pt, ¹¹⁹Sn), ²J(¹¹⁹Sn, ¹¹⁷Sn) and ²J(¹¹⁹Sn, ¹³C) data are given. A trans influence series, based on ¹J(¹⁹⁵Pt, ¹¹⁹Sn), reveals the following sequence: H^? > PR₃ > AsR₃ > SnCl₃^? > olefin > Cl^?.     

Carbon-13 nuclear magnetic resonance studies of creatine,creatinine and some of their analogs

Creatine (N-methyl-N-amidinoglycine), creatinine (1-methyl-2-aminoimidazolin-4-one) and a series of 38 of their close structural analogs have been examined using natural abundance ¹³C NMR spectroscopy at 25.16 MHz. Both proton-coupled and proton noise-decoupled spectra were recorded. Unequivocal assignments of the carbon resonances could be made in the vast majority of cases. Both ¹³C NMR chemical shifts and ¹J(CH) values can be used to characterize and to differentiate readily between analogs of creatine and analogs of creatinine. For example, the ¹J(CH) coupling constants for the α-carbons of the acyclic creatine analogs were all in the 140–142 Hz range, whereas the corresponding coupling constants for the related, cyclized creatinine analogs were all in the 150–152 Hz range.     

The 1H NMR spectra of some norbornene derivatives,a LIS study

The ¹H NMR spectra of 2-exo-hydroxymethyl-3-endo-methylnorbornene and the corresponding 2-endo-3-exo isomer have been completely assigned with the aid of lanthanide reagents. This enabled a full analysis of the unusual spectrum of 2-exo-hydroxy-methyl-3-endo-methylnorbornene to be undertaken, confirming the proposed structure. The ΔEu values for 2-exo-hydroxymethyl-3-endo-methylnorbornene and the 2-endo-3-exo-isomer have been used to test the effect of rotational averaging on the calculated pseudo contact shifts. Good agreement is obtained for a dynamic model in which the Eu atom exchanges between two sites on the oxygen atom of the OH bond, and in which the rotational equilibrium about the CH? CH₂OH bond is explicitly considered.