2 resultados para Competitive Displacement

em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo (BDPI/USP)


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New results for attenuation and damping of electromagnetic fields in rigid conducting media are derived under the conjugate influence of inertia due to charge carriers and displacement current. Inertial effects are described by a relaxation time for the current density in the realm of an extended Ohm`s law. The classical notions of poor and good conductors are rediscussed on the basis of an effective electric conductivity, depending on both wave frequency and relaxation time. It is found that the attenuation for good conductors at high frequencies depends solely on the relaxation time. This means that the penetration depth saturates to a minimum value at sufficiently high frequencies. It is also shown that the actions of inertia and displacement current on damping of magnetic fields are opposite to each other. That could explain why the classical decay time of magnetic fields scales approximately as the diffusion time. At very small length scales, the decay time could be given either by the relaxation time or by a fraction of the diffusion time, depending on whether inertia or displacement current, respectively, would prevail on magnetic diffusion.

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The reaction of cis-[RuCl(2)(P-P)(N-N)] type complexes (P-P = 1,4-bis(diphenylphosphino)butane or (1,1`-diphenylphosphino)ferrocene; N-N = 2,2`-bipyridine or 1,10-phenantroline) with monodentate ligands (L), such as 4-methylpyridine, 4-phenylpyridine and benzonitrile forms [RuCl(L)(P-P)(N-N)](+) species Upon characterization of the isolated compounds by elemental analysis, (31)P{(1)H} NMR and X-ray crystallography it was found out that the type of the L ligand determines its position in relation to the phosphorus atom. While pyridine derivatives like 4-methylpyridine and 4-phenylpyridine coordinate trans to the phosphorus atom, the benzonitrile ligand (bzCN), a good pi acceptor, coordinates trans to the nitrogen atom. A (31)P{(1)H} NMR experiment following the reaction of the precursor cis-[RuCl(2)(dppb)(phen)] with the benzonitrile ligand shows that the final position of the entering ligand in the complex is better defined as a consequence of the competitive effect between the phosphorus atom and the cyano-group from the benzonitrile moiety and not by the trans effect. In this case, the benzonitrile group is stabilized trans to one of the nitrogen atoms of the N-N ligand. A differential pulse voltammetry experiment confirms this statement. In both experiments the [RuCl(bzCN)(dppb)(phen)]PF(6) species with the bzCN ligand positioned trans to a phosphorus atom of the dppb ligand was detected as an intermediate complex. (c) 2009 Elsevier Ltd. All rights reserved.