| 1. |
- Erdelyi, Mate, 1975, et al.
(författare)
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Dynamics of the Glycosidic Linkage: Conformational Space of Lactose
- 2011
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Ingår i: Chemistry - A European Journal. - : Wiley. - 1521-3765 .- 0947-6539. ; 17:34, s. 9280-9282
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Tidskriftsartikel (refereegranskat)abstract
- Abstract: The dynamics of the glycosidic bond of lactose was studied by a paramagnetic tagging-based NMR technique, which allowed the collection of an unusually large series of NMR data for a single compound. By the use of distance- and orientation-dependent residual dipolar couplings and pseudocontact shifts, the simultaneous fitting of the probabilities of computed conformations and the orientation of the magnetic susceptibility tensor of a series of lanthanide complexes of lactose show that its glycosidic bond samples syn/syn, anti/syn and syn/anti f/y regions of the conformational space in water. The analysis indicates a higher reliability of pseudocontact shift data as compared to residual dipolar couplings with the presently available weakly orienting paramagnetic tagging technique. The method presented herein allows for an improved understanding of the dynamic behaviour of oligosaccharides.
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| 2. |
- Schmitt, H., et al.
(författare)
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Synthesis, redox properties, and EPR spectroscopy of manganese(III) complexes of the ligand N,N-bis(2-hydroxybenzyl)-N '-2-hdroxybenzylidene-1,2-diaminoethane : Formation of mononuclear, dinuclear, and even higher nuclearity complexes
- 2002
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 8:16, s. 3757-3768
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Tidskriftsartikel (refereegranskat)abstract
- The synthesis and characterization of the title trisphenolate ligand are described. From its reaction with manganese(iii) three complexes were isolated. The crystal structures revealed one pentacoordinate monomer and two similar dimers with different solvents of crystallization. In the dimers the metal ions are hexacoordinate and connected through bridging of two phenolates. A combination of electrochemistry and EPR spectroscopy showed that, in acetonitrile, the isolated batches were all identical and mainly monomeric, indicating that the mononuclear complex is in equilibrium with the dimer and perhaps also with complexes of higher nuclearity, as suggested by the detection of both the trimer and the tetramer by electrospray ionization mass spectrometry (ESI-MS). The successful use of the monomer batch as an epoxidation catalyst indicated that a high-valent manganese-oxo species can be formed, although it is probably short-lived. This is also suggested by EPR studies of the species formed by electrochemical oxidation of the complex. Upon one-electron oxidation, a manganese(iv) species was formed, which was at least partly converted to another species containing a phenoxy radical.
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| 3. |
- Brandt, Peter, et al.
(författare)
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Chromium-salen-mediated alkene epoxidation : a theoretical and experimental study indicates the importance of spin-surface crossing and the presence of a discrete intermediate.
- 2002
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 8:18, s. 4299-307
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Tidskriftsartikel (refereegranskat)abstract
- The mechanism of alkene epoxidation by chromium(v) oxo salen complexes has been studied by DFT and experimental methods. The reaction is compared to the closely related Mn-catalyzed process in an attempt to understand the dramatic difference in selectivity between the two systems. Overall, the studies show that the reactions have many similarities, but also a few critical differences. In agreement with experiment, the chromium system requires a change from low- to high-spin in the catalytic cycle, whereas the manganese system can proceed either with spin inversion or entirely on the high-spin surface. The low-spin addition of metal oxo species to an alkene leads to an intermediate which forms epoxide either with a barrier on the low-spin surface or without a barrier after spin inversion. Supporting evidence for this intermediate was obtained by using vinylcyclopropane traps. The chromium(v) oxo complexes can adopt a stepped shape or form a more concave surface, analogous to previous results on manganese salen complexes.
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| 4. |
- Gawronski, J., et al.
(författare)
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Novel Chiral Pyromellitdiimide (1,2,4,5-Benzenetetracarboxydiimide) Dimers and Trimers: Exploring Their Structure, Electronic Transitions and Exciton Coupling
- 2002
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Ingår i: Chemistry - A European Journal. - 1521-3765 .- 0947-6539. ; 8, s. 2484-2494 and ibid. 2833
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Tidskriftsartikel (refereegranskat)abstract
- The chiral but highly symmetrical acyclic and cyclic pyromellitic diimide dimers and trimers 2-5 have been obtained and characterized for the first time. The pyromellitdiimide chromophores in these molecules are linked by a rigid diequatorially 1,2-disubstituted cyclohexane skeleton. The structures of the compounds have been determined in detail by molecular modeling and, in the case of cyclic dimer 4 and trimer 5, by means of X-ray diffraction analysis. The electronically excited states of the pyromellitdiimide chromophore (1a) have been studied in these and other model compounds by means of linear dichroism (LD), magnetic circular dichroism (MCD), and circular dichroism (CD) spectroscopy. CD spectra of the rigid cyclic trimer 5 have provided the most detailed information on the excited states of the pyromellitdiimide chromophore. The low-energy tail (340-360 nm) of the absorption envelope can be assigned to out-of-plane polarized n-pi* transitions (I, II). The higher energy bands are due to contributions from up to six pi-pi* transitions, these being polarized either along the long (IV-VI, VIII) or short axis (III, VII). The results of ab initio CIS/cc-pVDZ and semiempirical INDO/S-CI calculations have been compared with the experimental data. CD Cotton effects in the region 200260 nm, which result from exciton interactions between electric dipole allowed transitions of two pyromellitdiimide chromophores in compounds 2-5, provide reliable and useful information concerning the conformation and absolute configuration of these molecules, which may be extrapolated to other oligoimide systems.
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| 5. |
- Goeppert, Alain, et al.
(författare)
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Methane activation and oxidation in sulfuric acid
- 2002
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 8:14, s. 3277-3283
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Tidskriftsartikel (refereegranskat)abstract
- The H/D exchange observed when methane is contacted with D(2)SO(4) at 270-330 degrees C shows that the alkane behaves as a sigma base and undergoes rapid and reversible protonation at this temperature. DFT studies of the hydrogen exchange between a monomer and a dimer of sulfuric acid and methane show that the transition states involved in the exchange are bifunctional, that is one hydrogen atom is transferred from a hydroxy group in sulfuric acid to methane, while one hydrogen atom is abstracted from methane by a non-hydroxy oxygen atom in sulfuric acid. All the transition states include a CH(5) moiety, which shows similarities to the methanium ion CH(5) (+). The calculated potential activation energy of the hydrogen exchange for the monomer is 174 kJ mol(-1), which is close to the experimental value (176 kJ mol(-1)). Solvation of the monomer and the transition state of the monomer with an extra sulfuric acid molecule, decrease the potential activation energy by 6 kJ mol(-1). The acid-base process is in competition, however, with an oxidative process involving methane and sulfuric acid which leads to CO(2), SO(2), and water, and thus to a decrease of acidity and loss of reactivity of the medium.
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| 6. |
- Jalilehvand, F., et al.
(författare)
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Tl-Pt(CN)(5) in the solid state - A multimethod study of an unusual compound containing inorganic wires
- 2001
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 7:10, s. 2167-2177
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Tidskriftsartikel (refereegranskat)abstract
- The crystal and molecular structure of a polycrystalline powder with a metal-metal bond and the composition TlPt(CN)(5) has been determined by combining results from X-ray powder diffraction (XRD), extended X-ray absorption fine structure (EXAFS) and vibrational spectroscopic studies. The XRD data gave the tetragonal space group P4/nmm (No. 129). with a = 7.647(3), c = 8.049(3) Angstrom, Z = 2, and well-determined positions of the heavy metal atoms. The Pt-Tl bond length in the compound is 2.627(2) Angstrom. The platinum atom coordinates four equivalent equatorial cyano ligands, with a fifth axial CN ligand and a thallium atom completing a distorted octahedral coordination geometry. The Tl-Pt(CN)(5) entities are linked together in linear -NC-Pt-Tl-NC-Pt-Tl chains through the axial cyano ligand. These linear wires are the essential structural features and influence the properties of the com-pound. A three-dimensional network is formed by the four equatorial cyano ligands of the platinum atom that form bridges to the thallium atoms of neighbouring antiparallel chains. The platinum atom and the five nitrogen atoms from the bridging cyano groups form a distorted octahedron around the thallium atom. EXAFS data were recorded at the Pt and Tl L-III edges for a more complete description of the local structure around the Pt and Tl atoms. The excessive multiple scattering was evaluated by means of the FEFF program. Raman and infrared absorption spectroscopy reveal strong coupling of the vibrational modes of the TlPt(CN)(5) entities, in particular the metal - metal stretching mode, which is split into four Raman and two IR bands. Factor group theory shows that a structural unit larger than the crystallographic unit cell must be used to assign vibrational bands. Intra- and intermolecular force constants have also been calculated. The compound exhibits red luminescence at 700+/- 3 nm in glycerol and has a corresponding excitation maximum at 240 nm. X-ray photoelectron spectra (XPS) show that the metal atoms have intermediate oxidation states, Pt3.2+ and Tl1.6+, between those in the parent Pt-II and Tl-III species and the decomposition products, Pt-IV and Tl-I. The solid compound TlPt(CN)(5) is stable to 520 degreesC. However in presence of water, a two-electron transfer between the metal atoms results in the cleavage of the metal-metal bond at 80 degreesC, forming a Pt-IV pentacyanohydrate complex and a monovalent thallium ion.
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| 7. |
- Kilså, Kristine, et al.
(författare)
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Enhanced Intersystem Crossing in Donor/Acceptor Systems Based on Zinc/Iron or Free-Base/Iron Porphyrins
- 2001
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Ingår i: Chemistry, A European Journal. - 1521-3765 .- 0947-6539. ; 7:10, s. 2122-33
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Tidskriftsartikel (refereegranskat)abstract
- The deactivation pathways of the singlet excited state of a series of zinc or free-base donor porphyrins covalently linked by a bridge to a paramagnetic iron(iii) chloride porphyrin acceptor have been studied. These donor-bridge-acceptor systems all share a similar geometry (25 Å donor-acceptor center-to-center distance), but the bridges vary in electronic structure. In previously reported investigations of zinc/iron porphyrin systems, the fluorescence quenching of the donor has predominantly been assigned to electron transfer. However, for the porphyrin systems studied in this paper, we show that the dominant deactivation channels are enhanced intersystem crossing and singlet energy transfer. In both series, the intersystem crossing rate (S1T1) of the donor moiety is almost doubled in the presence of a paramagnetic high-spin metal-porphyrin acceptor. The significant spectral overlap of the donor fluorescence and acceptor absorption in both series allows for efficient singlet energy transfer (Förster mechanism). Furthermore, the bridging chromophores mediate energy transfer and the enhancement is inversely dependent upon the energy gap between the donor and bridge excited states. Although Marcus theory predicts thermodynamically favorable electron transfer to occur in the systems investigated, the quenching rate constants were found to be independent of solvent polarity, and no charge-separated state could be detected, indicating very small electronic coupling for electron transfer.Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2111/2001/f2779_s.pdf or from the author. 1H NMR spectra of FeP, FeP-OB, FeP-BB, FeP-NB, FeP-AB, ZnP-OB-FeP, ZnP-BB-FeP, ZnP-NB-FeP, and ZnP-AB-FeP.
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| 8. |
- Kuznetsov, Alexei N., et al.
(författare)
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Ab initio Calculations on Bismuth Cluster Polycations
- 2001
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 7:13, s. 2821-2828
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Tidskriftsartikel (refereegranskat)abstract
- Ab initio calculations on bismuth polycationic species of the types Bi-n((n-2)+), Bi-n((n-4)+), and Bi-n((n-6)+) (n = 3 -12) were performed at the Hartree -Fock and density functional theory levels in order to investigate their general properties and the applicability of Wade's rules on bismuth polycations. Some exceptions to Wade's rules were encountered, and, moreover, several predicted and calculated minima shaw only meta-stable behavior. The bonding in bismuth polycations is characterized by a high degree of electron delocalization and "three-dimensional aromaticity".
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| 9. |
- Lindström, U. M., et al.
(författare)
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Aza- 3,3 -claisen enolate rearrangement in vinylaziridines : Stereoselective synthesis of mono-, di-, and trisubstituted seven-membered lactams
- 2001
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 7:1, s. 94-98
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Tidskriftsartikel (refereegranskat)abstract
- Several 2,3-disubstituted vinylaziridines have been N-acylated and subjected to LiHMDS in THF at - 78 degreesC. Upon warming to room temperature, the resulting amide enolates underwent a highly stereoselective [3,3]-sigmatropic rearrangement to give mono-, di-, and trisubstituted seven-membered lactams in good yields. The scope and limitations of the process have been investigated by using variously substituted vinylaziridines. A kinetically controlled process proceeding through a six-membered boatlike transition state assembly has been invoked to explain the stereochemical outcome of the reaction.
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| 10. |
- Samec, Joseph S. M., et al.
(författare)
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Ruthenium-catalyzed transfer hydrogenation of imines by propan-2-ol in benzene.
- 2002
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Ingår i: Chemistry - A European Journal. - 0947-6539 .- 1521-3765. ; 8:13, s. 2955-2961
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Tidskriftsartikel (refereegranskat)abstract
- Transfer hydrogenation of a variety of different imines to the corresponding amines by propan-2-ol in benzene catalyzed by [Ru2(CO)4(Ό-H)(C4Ph4COHOCC4Ph4)] (1) has been studied. The reaction is highly efficient with turnover frequencies of over 800 per h, and the product amines were obtained in excellent yields. A remarkable concn. dependence of propan-2-ol was obsd. when the reaction was run in benzene as cosolvent. An optimum was obtained at 24 equiv of propan-2-ol to imine, and further increase of the propan-2-ol led to a dramatic decrease in rate. Also the use of polar cosolvents with 24 equiv of propan-2-ol gave a low rate. It was found that ketimines react faster than aldimines and that electron-donating substituents on the imine increase the rate of the catalytic transfer hydrogenation. Electron-withdrawing substituents decreased the rate. An isomerization was obsd. with imines having an α-hydrogen at the N-alkyl substituent, which is in accordance with a mechanism involving a ruthenium-amine intermediate. It was demonstrated that the ruthenium-amine complex from α-methylbenzylamine, corresponding to the postulated intermediate, can replace 1 as catalyst in the transfer hydrogenation of imines. A primary deuterium isotope effect of kCH/CD = 2.7 ± 0.25 was obsd. when 2-deuterio-propan-2-ol was used in place of propan-2-ol in the transfer hydrogenation of N-phenyl-(1-phenylethylidene)amine. [on SciFinder(R)]
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