Search results for "magnetic resonance spectroscopy"
showing 10 items of 1362 documents
Timolol derivatives. I. X-ray, NMR and theoretical studies of the crystallization of (S)-timolol O,O-diacetyl-l-tartaric acid monoester
1993
Abstract The absolute configurations of (S)-timolol hemihydrate and (S)-timolol O,O-diacetyl-(R,R)-tartaric acid monoester were determined by single crystal X-ray diffraction. An NMR analysis based on the temperature dependence of vicinal coupling constants was carried out to characterize the conformational behaviour of the S,R,R- and R,R,R-forms in solution. The same conformation as in crystalline state was also found in solution, although with a rather low preference over some other conformations. Results of theoretical calculations using MNDO and AMBER force field methods are reported. An infinite chain of hydrogen bonds, along with other favourable inter- and intramolecular forces that …
Oxidomolybdenum(IV), ‐(V), ‐(VI) Complexes with Relevance to Molybdenum Enzymes: Oxygen Atom Transfer, Redox Chemistry and EPR Spectroscopy
2010
The cis-dioxidomolybdenum(VI) complex Mo(NN′)2O2 (1) [(NN′) = N-(4-hydroxyphenyl)-2-pyrrolatocarbaldimine] transfers one oxygen atom to phosphanes PMenPh3–n (n = 0–3) to give quantitatively the respective phosphane oxides OPMenPh3–n (OAT, oxygen atom transfer). The kinetics of these OAT reactions has been investigated spectrophotometrically. When offering excess PMenPh3–n (n = 1–3), oxido(phoshane)molybdenum(IV) complexes Mo(NN′)2O(PMenPh3–n) 5a–5c are isolated and characterized by multinuclear NMR spectroscopy (1H, 13C, 31P, 15N), IR spectroscopy, UV/Vis spectroscopy and mass spectrometry. The redox chemistry of the molybdenum(IV) complexes 5a–5c and of molybdenum(VI) complex 1 has been pr…
Low-temperature methyl group dynamics of hexamethylbenzene in crystalline and glassy matrices as studied by 2H NMR
1991
Abstract 2 H NMR spectra of hexamethylbenzene (HMB) in protonated crystalline and amorphous matrices at low temperatures are presented. All spectra reveal lineshape changes which can be attributed to methyl group tunnelling. Compared to neat HMB, a drastic increase of the tunnelling frequency is found for all systems. This indicates that the hindering potential originates predominantly from intermolecular forces. We studied the temperature dependence of these spectra and the spin-lattice relaxation in order to exclude a distribution of motional correlation times describing a thermally activated process. In addition, we find a distortion of the methyl tetrahedron.
Reactions of Carbonyl Compounds in Basic Solutions. Part 351: The Alkaline Hydrolysis and Reactivity – Structure – Spectra Correlations of (Z)-4-(Sub…
2002
The kinetics of the alkaline hydrolysis and the configuration, conformation and electronic structure were studied using IR, NMR spectroscopy, X-ray analysis and AM1 theoretical calculations for a series of (Z)-4-(substituted benzylidene)-2-phenyl-4H-oxazol-5-ones (1) and compared with analogous results reported for (E)-4-benzylidene-2-phenyl-4H-furan-5-ones (5) and related compounds.
Synthesis, X-ray crystal structure, NMR characterization and theoretical calculations on [Cp2Ta(η2-H2)(CO)]+, the first thermally stable group 5 dihy…
2001
Protonation of Cp2TaH(CO) (Cp = C5H5, 1a; C5H4But, 1b) by HBF4·Et2O at −78 °C in CH2Cl2 affords [Cp2TaH2(CO)]BF4 (2, 3) as mixtures of 2 isomers. The minor ones (2a, 2b) contain the known trans-dihydride [Cp2TaH2(CO)]+ cations whereas the major ones (3a, 3b) are [Cp2Ta(η2-H2)(CO)]BF4, the first group 5 dihydrogen complexes. The crystal structure of the analogous complex 3a·BArf4 recorded at 120 K confirms the presence of the coordinated dihydrogen ligand, which displays an H–H separation of 1.09(2) A in agreement with distances calculated from NMR data. Protonation of Cp2TaH2(SiMe2Ph) by (Et2O)2 ·HBArf4 does not lead to an analogous silane derivative but to the new dinuclear complex [(Cp2…
Aggregation versus Biological Activity in Gold(I) Complexes. An Unexplored Concept
2021
The aggregation process of a series of mono- and dinuclear gold(I) complexes containing a 4-ethynylaniline ligand and a phosphane at the second coordination position (PR3-Au-C≡CC6H4-NH2, complexes 1-5, and (diphos)(Au-C≡CC6H4-NH2)2, complexes 6-8), whose biological activity was previously studied by us, has been carefully analyzed through absorption, emission, and NMR spectroscopy, together with dynamic light scattering and small-angle X-ray scattering. These experiments allow us to retrieve information about how the compounds enter the cells. It was observed that all compounds present aggregation in fresh solutions, before biological treatment, and thus they must be entering the cells as a…
A 4-tert-butylcalix[4]arene tetrahydroxamate podand based on the 1-oxypiperidine-2-one (1,2-PIPO−) chelate. Self-assembly into a supramolecular ionop…
2014
An octadentate tetrahydroxamic calix[4]arene podand incorporating 1-hydroxypiperidine-2-one (1,2-PIPOH) binding units has been designed as a specific chelator for tetravalent metal cations like Zr4+ or Hf4+. This receptor, which can be considered as the first ever abiotic ligand possessing only cyclic six-membered hydroxamate groups, has been synthesized and characterized in its tetraprotonated form (1H4). Contrary to expectation, however, this new chelator did not form a 1 : 1 complex upon reaction with M(acac)4 (M = Zr and Hf; acac = acetylacetonate), but rather self-assembled into a dimeric species of 2 : 2 stoichiometry. The latter could be characterized in solution by mass spectrometry…
CPMAS 13C NMR Characterization of Leaves and Litters from the Reafforestated Area of Mustigarufi in Sicily (Italy)
2010
Reafforestation is generally based on the planting of exotic fast growing tree species suitable for adapting to even harsh environments. Once the introduced plants ameliorate soil conditions, they can be progressively replaced by au- tochthonous plant species. Reafforestation is applied worldwide. However, only few studies on the effect of reafforesta- tion on lands from Mediterranean regions are available. This paper reports the characterization by cross polarization 13C NMR spectroscopy of fresh leaves and superficial litters from a reafforestated area in central Sicily (Italy). NMR assign- ment is attempted. A differentiation among the molecular systems within leaves and litters is also …
More insight into characterization of the waterlogged wooden part of Acqualadroni Roman Rostrum by solid-state NMR
2016
Abstract Solid-state NMR spectroscopy was applied to characterize the wooden part of a roman Rostrum recovered in the Tyrrhenian Sea in the Acqualadroni area (Messina, Italy). The Acqualadroni Rostrum has been, in the recent past, investigated to establish its provenance and conservation. In this paper, solid-state NMR was used to obtain information on the conservation state of the wood as a preliminary step for the conservation process. A wooden sample of this artifact, collected by coring, was divided in four parts in order to correlate the conservation state to the depth. Results were compared with those obtained for a modern wood of the same species. A structural study was performed by …
Radical cations and dications of bis[1]benzothieno[1,4]thiazine isomers
2021
Bis[1]benzothieno[1,4]thiazines (BBTT) are particularly electron-rich S,N-heteropentacenes and their radical cations and dications can be relevant intermediates in charge transport materials. All three regioisomers of N-p-fluorophenyl-BBTT (syn–syn, syn–anti, and anti–anti) were studied. A reliable preparation of radical cations and dications using antimony pentachloride as an oxidant gives deeply colored salts. The electronic structure of the radical cations was assessed by EPR spectroscopy, whereas dicationic structures were characterized by NMR spectroscopy. In addition, a deeper insight into the electronic structure was experimentally and computationally obtained by UV/Vis spectroscopy …