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Dipl.‐Chem. Alexander Zhdanko Dr. Markus Ströbele Prof. Dr. Martin E. Maier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14732-14744
Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh3, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf??Me2S<2,6‐lutidine<4‐picoline<CF3CO2?≈DMAP<TMTU<PPh3<OH?≈Cl?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)2 and S‐tolBINAP(AuOTf)2 showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh3 causes abstraction of one gold atom to give mononuclear complexes LLAuPPh3+ and (Ph3P)nAu+, but other N and S ligands give ordinary dicationic species LL(AuNu)22+. In reactions with different bases, LAu+ provided new oxonium ions whose chemistry was also studied: (DTBPAu)3O+, (L2Au)2OH+, (L2Au)3O+, (L3Au)2OH+, and (IMesAu)2OH+. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)2OH+, (L2Au)3O+, and L2AuOH are described. Reactions of dppf(AuOTf)2 and S‐tolBINAP(AuOTf)2 with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)2]3O22+, L8(Au)2OH+, and [L8(Au)2]3O22+, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe+ with S2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined. 相似文献
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V. V. Glagolev R. M. Lebedev G. D. Pestova S. S. Shimansky M. Kravčíková M. Seman L. Šándor A. Dirner J. Hlaváčová G. Martinská J. Urbán K. U. Khairetdinov H. Braun J. P. Gerber P. Juillot A. Michalon A. K. Kacharava Z. P. Menteshashvili N. S. Nioradze Z. R. Salukvadze T. Sobczak J. Stepaniak 《Zeitschrift fur Physik C Particles and Fields》1993,60(3):421-425
4He-p collisions at two values of4He momenta 8.6 GeV/c and 13.6 GeV/c as well as the3He-p collisions at 13.5 GeV/c have been studies using the one-meter JINR hydrogen bubble chamber. Total, elastic, topological and reaction cross sections have been measured. The cross sections have been determined on a sample of minimum biased events. 相似文献
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Negative electrorheological responses induced by micro-particle electrorotation in two-dimensional Couette flow geometries are analyzed by a set of continuum modeling field equations originating from anti-symmetric/couple stress theories in the finite spin viscosity small spin velocity (FSV) limit. Analytical solutions are obtained for the first time to express the spin velocity, linear velocity, and effective viscosity in terms of the electric field strength, driving shear rate, boundary condition selection parameter, and spin viscosity. Good agreement is achieved between the FSV theoretical predictions presented herein and the experimental measurements reported in recent literature for the effective viscosity for low driving shear rates. 相似文献
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This paper describes band structure computations of photonic crystals with a hexagonal lattice. Particularly, the full vectorial three-dimensional case is considered. The unit cells are approximated with a staircase approximation. Due to their periodicity, fields inside the computational window can be related to those outside of this area. Numerical results are compared with those from the literature and show a very good agreement. 相似文献