Fluorierung von Cyanurchlorid und Tieftemperatur-Kristallstruktur von [(ClCN)3F]+ [AsF6]−

Fluorination of Cyanuric Chloride and Low-Temperature Crystal Structure of [(ClCN)₃F]⁺[AsF₆]^? The low-temperature fluorination of cyanuric chloride, (ClCN)₃, with F₂/AsF₅ in SO₂F₂ solution yielded the salt [(ClCN)₃F]⁺ [AsF₆]^? ( 1 ) essentially in quantitative yield. Compound 1 was identified by a low-temperature single crystal X-ray structure determination: R 3 c, trigonal, a = b = 10.4246(23) Å, c = 15.1850(24) Å, V = 1429.1(4) Å 3, Z = 6, R_F = 0.056, R_w = 0.076 (for significant reflections), R_F = 0.088, R_w = 0.079 (for all reflections). Fluorination of neat (ClCN)₃ with [NF₄]⁺ [Sb₂F₁₁]^? yielded NF₃, CClF₃, SbF₃, N₂ and traces of CF₄. A qualitative scale for the oxidizing strength of the oxidative fluorinators NF₄⁺ and (XCN)₃F⁺ (X = H, F, Cl) has been computed ab initio.     

Random-phase-approximation-based correlation energy functionals: benchmark results for atoms

The random phase approximation for the correlation energy functional of the density functional theory has recently attracted renewed interest. Formulated in terms of the Kohn-Sham orbitals and eigenvalues, it promises to resolve some of the fundamental limitations of the local density and generalized gradient approximations, as, for instance, their inability to account for dispersion forces. First results for atoms, however, indicate that the random phase approximation overestimates correlation effects as much as the orbital-dependent functional obtained by a second order perturbation expansion on the basis of the Kohn-Sham Hamiltonian. In this contribution, three simple extensions of the random phase approximation are examined; (a) its augmentation by a local density approximation for short-range correlation, (b) its combination with the second order exchange term, and (c) its combination with a partial resummation of the perturbation series including the second order exchange. It is found that the ground state and correlation energies as well as the ionization potentials resulting from the extensions (a) and (c) for closed subshell atoms are clearly superior to those obtained with the unmodified random phase approximation. Quite some effort is made to ensure highly converged data, so that the results may serve as benchmark data. The numerical techniques developed in this context, in particular, for the inherent frequency integration, should also be useful for applications of random phase approximation-type functionals to more complex systems.     

Electronic structure of neutral and monoanionic tris(benzene-1,2-dithiolato)metal complexes of molybdenum and tungsten

The reaction of 3 equiv of the ligand 2-mercapto-3,5-di-tert-butylaniline, H2[LN,S], or 3,5-di-tert-butyl-1,2-benzenedithiol, H2[LS,S], with 1 equiv of [MoO2(acac)2] or WCl6 (acac=acetonylacetate(1-)) in methanol or CCl4 afforded the diamagnetic neutral complexes [MoV(LN,S)2(L*N,S)]0 (1), [MoV(LS,S)2(L*S,S)] (2), and [WV(LS,S)2(L*S,S)] (3), where (L*N,S)- and (L*S,S)- represent monoanionic pi-radical ligands (Srad=1/2), which are the one-electron oxidized forms of the corresponding closed-shell dianions (LN,S)2- and (LS,S)2-. Complexes 1-3 are trigonal-prismatic members of the electron-transfer series [ML3]z (z=0, 1-, 2-). Reaction of 2 and 3 with [N(n-Bu)4](SH) in CH2Cl2 under anaerobic conditions afforded paramagnetic crystalline [N(n-Bu)4][MoV(LS,S)3] (4) and [N(n-Bu)4][WV(LS,S)3] (5). Complexes 1-5 have been characterized by X-ray crystallography. S K-edge X-ray absorption and infrared spectroscopy prove that a pi-radical ligand (L*S,S)- is present in neutral 2 and 3, whereas the monoanions [MV(LS,S)3]- contain only closed-shell dianionic ligands. These neutral species have previously been incorrectly described as [MVI(L)3]0 complexes with a MoVI or WVI (d0) central metal ion; they are, in fact MV (d1) (M=Mo, W) species: [MoV(LS,S)2(L*S,S)] and [WV(LS,S)2(L*S,S)] with a diamagnetic ground state St=0, which is generated by intramolecular, antiferromagnetic coupling between the MV (d1) central ion (SM=1/2) and a ligand pi radical (L*S,S)- (Srad=1/2).     

Iron complexes of new pentadentate ligands containing the 1,4,7-triazacyclononane-1,4-diacetate motif. spectroscopic, electro-, and photochemical studies

Three new pentadentate, pendent arm macrocycles containing the 1,4,7-triazacyclononane-1,4-diacetate motif have been synthesized, and their coordination chemistry with Fe(III) has been investigated. Eight new octahedral Fe(III) complexes containing chloro, azido, or mu-oxo ligands have been synthesized, five of which have been characterized by X-ray crystallography. Spectroscopic characterization of these octahedral Fe(III) complexes by UV-vis, IR, electrochemistry, EPR, magnetic susceptibility, and zero-field M?ssbauer measurements firmly establishes the high-spin state of the iron in all complexes. Electrochemistry studies of the azido-Fe(III) complexes show that they can be reversibly oxidized to the corresponding Fe(IV) species at -20 degrees C, and Fe(II), Fe(III), and Fe(IV) species show characteristic IR and UV-vis profiles. Photolysis of one of the azido complexes was studied as a function of temperature (room temperature vs 77 K) and wavelength (480, 419, and 330 nm). Photoreduction to a high-spin Fe(II) species occurs under all conditions, which is proposed to be the dominant photochemical pathway generally available to high-spin ferric azido complexes.     

SINGLE- and DOUBLE-STRAND BREAK FORMATION IN DOUBLE-STRANDED DNA UPON NANOSECOND LASER-INDUCED PHOTOIONIZATION

Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA.     

Electronic structures of tris(dioxolene)chromium and tris(dithiolene)chromium complexes of the electron-transfer series [Cr(dioxolene)(3)](z) and [Cr(dithiolene)(3)](z) (z = 0, 1-, 2-, 3-). A combined experimental and density functional theoretical study

From the reaction mixture of 3,6-di-tert-butylcatechol, H2[3,6L(cat)], [CrCl3(thf)3], and NEt3 in CH3CN in the presence of air, the neutral complex [CrIII(3,6L*(sq))3] (S = 0) (1) was isolated. Reduction of 1 with [Co(Cp)2] in CH2Cl2 yielded microcrystals of [Co(Cp)2][CrIII(3,6L*(sq))2(3,6L(cat))] (S = 1/2) (2) where (3,6L*(sq)(1-) is the pi-radical monoanionic o-semiquinonate of the catecholate dianion (3,6Lcat)(2-). Electrochemistry demonstrated that both species are members of the electron-transfer series [Cr(3,6LO,O)]z (z = 0, 1-, 2-, 3-). The corresponding tris(benzo-1,2-dithiolato)chromium complex [N(n-Bu)4][CrIII(3,5L*S,S)2(3,5LS,S)] (S = 1/2) (3) has also been isolated; (3,5LS,S)(2-) represents the closed-shell dianion 3,5-di-tert-butylbenzene-1,2-dithiolate(2-), and (3,5L*S,S)(1-) is its monoanionic pi radical. Complex 3 is a member of the electron-transfer series [Cr(3,5L(S,S))3]z (z = 0, 1-, 2-, 3-). It is shown by Cr K-edge and S K-edge X-ray absorption, UV-vis, and EPR spectroscopies, as well as X-ray crystallography, of 1 and 3 that the oxidation state of the central Cr ion in each member of both electron-transfer series remains the same (+III) and that all redox processes are ligand-based. These experimental results have been corroborated by broken symmetry density functional theoretical calculations by using the B3LYP functional.     

A Fast and Efficient Track to Allosteric Modulators of Muscarinic Receptors: Microwave-Assisted Syntheses

By using microwave irradiation bisammonium-and bispyridinium-type allosteric modulators of muscarinic receptors can be obtained fast and efficiently.     

Inhibition of UV-induced immune suppression and interleukin-10 production by plant oligosaccharides and polysaccharides

Application of Aloe barbadensis poly/oligosaccharides to UV-irradiated skin prevents photosuppression of delayed-type hypersensitivity (DTH) responses in mice. We tested the hypothesis that these carbohydrates belong to a family of biologically active, plant-derived polysaccharides that can regulate responses to injury in animal tissues. C3H mice were exposed to 5 kJ/m2 UVB from unfiltered FS40 sunlamps and treated with between 1 pg and 10 micrograms tamarind xyloglucans or control polysaccharides methylcellulose or dextran in saline. The mice were sensitized 3 days later with Candida albicans. Tamarind xyloglucans and purified Aloe poly/oligosaccharides prevented suppression of DTH responses in vivo and reduced the amount of interleukin (IL)-10 observed in UV-irradiated murine epidermis. Tamarind xyloglucans were immunoprotective at low picogram doses. In contrast, the control polysaccharides methylcellulose and dextran had no effect on immune suppression or cutaneous IL-10 at any dose. Tamarind xyloglucans and Aloe poly/oligosaccharides also prevented suppression of immune responses to alloantigen in mice exposed to 30 kJ/m2 UVB radiation. To assess the effect of the carbohydrates on keratinocytes, murine Pam212 cells were exposed to 300 J/m2 UVB radiation and treated for 1 h with tamarind xyloglucans or Aloe poly/oligosaccharides. Treatment of keratinocytes with immunoprotective carbohydrates reduced IL-10 production by approximately 50% compared with the cells treated with UV radiation alone and completely blocked suppressive activity of the culture supernatants in vivo. The tamarind xyloglucans also blocked UV-activated phosphorylation of SAPK/JNK protein but had no effect on p38 phosphorylation. These results indicate that animals, like plants, may use carbohydrates to regulate responses to environmental stimuli.     

HPLC-NMR of fatty alcohol ethoxylates

The application of HPLC-NMR for the analysis of a mixture of fatty alcohol ethoxylates (FAEs) is described. The use of the new generation, cryogenically cooled probes is investigated in respect of the sensitivity advantage that they provide. The FAE mixture is separated using liquid chromatography at the critical point of adsorption. The ability of the method to differentiate between the different end groups and the degree of polymerization of the mixture constituents is investigated. Both on-flow and stop-flow HPLC-NMR techniques were used together with two-dimensional NMR spectroscopy. The results are compared with those obtained by using an evaporative light scattering detector for the HPLC.