Search results for "MR"
showing 10 items of 3001 documents
Simulation of13C NMR chemical shifts for polychlorinated and polybrominated oxybenzenes with two-particle increment scheme
1994
A two-particle system of OY-Cl and OY-Br mixed increments for predicting13C NMR chemical shifts of polyhalogenated polyoxybenzenes has been developed. It has been found that only theortho- and para-interactions of the OY and Hal substituents contribute significantly to the13C chemical shifts and that theortho-effects of the OY located between Ha1 and H and those of the OY located between two Ha1 atoms are different. Additional effects are due to solvating solvents. The increment scheme is predictive over the whole class of compounds under consideration and may be realized on personal computers.
DFT calculations of structures, 13C NMR chemical shifts, and Raman RBM mode of simple models of small-diameter zigzag (4,0) carboxylated single-walle…
2012
Linearly conjugated benzene rings (acenes), belt-shaped molecules (cyclic acenes), and models of single-walled carbon nanotubes (SWCNTs) with one carboxylic group at the open end were fully optimized at the B3LYP/6-31G* level of theory. These models were selected to obtain some insight into the nuclear isotropic changes resulting from systematically increasing the basic building units of open-tip-monocarboxylated SWCNTs. In addition, the position of radial breathing mode (RBM), empirically correlated with the SWCNT diameter, was directly related with the radius of model cyclic acene rings. A regular convergence of selected structural, NMR, and Raman parameters with the molecular system size…
GIAO/DFT calculated chemical shifts of tautomeric species. 2-Phenacylpyridines and (Z)-2-(2-hydroxy-2-phenylvinyl)pyridines
2001
1H, 13C and 15N NMR chemical shifts for 28 substituted 2-phenacylpyridines (ketimine forms) and their enolimine tautomers, (Z)-2-(2-hydroxy-2-phenylvinyl)pyridines, were calculated via the GIAO/DFT approach. Among four tested methods at the B3LYP level of theory, the 6–311G, 6–311++G and 6–311G** basis sets gave acceptable result for 13C NMR chemical shifts whereas the 6–311++G** basis set was the minimum needed for reproduction of 15N NMR chemical shifts. Satisfactory reproduction of 13C and 15N NMR chemical shifts for different tautomers revealed that intramolecular hydrogen bonding could be modeled reliably by these calculations when the geometry optimizations were done with the HF/3–21G…
NMR spectroscopy in environmental chemistry:1H and13C NMR parameters of tricyclic polychlorinated C10 hydrocarbons and their oxy derivatives based on…
1999
Two-dimensional homo- and heteronuclear NMR chemical shift correlation techniques were applied in the characterization of five tricyclic polychlorinated C10 hydrocarbons, chlordene (1), heptachlor (2), trans-nonachlor (3), α-chlordene (4) and γ-chlordene (5), which are spread globally in the environment owing to their use as insecticides. Approximate and partly contradictory 1H and 13C NMR chemical shifts reported in the literature were corrected in this work. The chemical shift assignments of 1–5 were based on DQF COSY, HMQC and HMBC experiments. In addition, an INADEQUATE experiment was needed to ascertain the 13C chemical shifts assignment of 2. The nJ(H,H)s of 1–5 were solved by compute…
Synthesis and 1H-NMR configurational study of δ3-thiazolines from 2-aza-1,3-dienes
1992
Abstract A [4+1] heterocyclization process involving 2-aza-1,3-dienes and elemental sulphur leading to the synthesis of Δ3-thiazolines with excellent yields is described. A 1D TOCSY and 1D NOESY study of these systems was made in order to establish the configurations of the diastereoisomeric mixture.
1,6-π-Electrocyclization of 3-Vinyl-FunctionalizedN,N-Dimethyl-2,2′-Bisindolyl: Some analysis of the educt transformation process
1998
The thermally and photochemically induced 1,6-π-electrocyclization reaction of 3-vinyl-functionalized N, N'-dimethyl-2,2′-bisindolyls 4 has been analysed and some reactivity aspects are presented. On the basis of time dependent 1H nmr and uv spectroscopic measurements the educt transformations can be observed in detail. Some results of the isomerization process of the educts are also given.
Preparation and structural studies on dibutyltin(IV) complexes with pyridine mono- and dicarboxylic acids
2004
Abstract A number of organotin(IV) complexes with pyridine mono- and dicarboxylic acids (containing ligating –COOH group(s) and aromatic {N} atoms) were prepared in the solid state. The bonding sites of the ligands were determined by means of FT-IR spectroscopic measurements. It was found that in most cases the –COO− groups form bridges between two central {Sn} atoms, thereby leading to polymeric (oligomeric) complexes. On this basis, the experimental 119Sn Mossbauer spectroscopic data were treated with partial quadrupole splitting approximations. The calculations predicted the existence of complexes with octahedral (oh) and trigonal-bipyramidal (tbp) structures, but the formation of comple…
Structural relaxation in a molten salt probed by time-dependent dc conductivity measurements
1998
Abstract Time-dependent dc conductivity was measured after cooling steps of about 2 K in the glass transformation range of 2Ca(NO 3 ) 2 -3RbNO 3 . The shape and time scale of the structural relaxation function was thus monitored for times 60 s t 6 s. The time scale could be compared with results from scanning calorimetry measurements and good agreement was found. From the heat capacity data and from the solid state conductivity the expected liquid state conductivity relaxation time was calculated using several models. The good compatibility of these calculations with the experimental results provides evidence that near the calorimetric glass transition the mobile ions perform concerted moti…
Thermal behaviour and electrochemical properties of bis(trifluoromethanesulfonyl)amide and dodecatungstosilicate viologen dimers
2012
We report the synthesis and characterization of dimeric viologen salts (1',1''-(alkane-1,n-diyl)bis(1-ethyl-4,4'-bipyridinium) with n = 4-10) with bis(trifluoromethanesulfonyl)amide (bistriflimide, Tf(2)N(-)) as a counteranion. For n = 4, 5 and 6, and for the nonylviologen cation (1,1'-dinonyl-4,4'-bipyridinium) we also prepared salts with the totally inorganic dodecatungstosilicate anion, SiW(12)O(40)(4-), featuring a poly-charged surface and nanosized dimensions. The materials have been characterized by means of calorimetric techniques, X-ray diffraction and solid state NMR and a comparison is made with analogous monomeric viologen salts exhibiting smectic mesophases. A strong odd-even ef…
Cooperatively Enhanced Ion Pair Binding with a Hybrid Receptor
2015
A simple 18-crown-6-based bis-urea receptor R(1) was synthesized in three steps from a commercial starting material. The receptor's behavior toward anions, cations, and ion pairs was studied in solution with (1)H NMR, in solid state with single-crystal X-ray diffraction, and in gas phase with mass spectrometry. In 4:1 CDCl3/dimethyl sulfoxide solution the receptor's binding preference of halide anions is I(-) < Br(-) < Cl(-) following the trend of the hydrogen-bonding acceptor ability of the anions. The receptor shows a remarkable positive cooperativity toward halide anions Cl(-), Br(-), and I(-) when complexed with Na(+), K(+), or Rb(+). The solid-state binding modes of R(1) with alkali an…