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The 57Fe Mössbauer effect in [Fe(pythiaz)2] (BF4)2 (I) and [Fe(pythiaz)2] (C&O4)2 (II) has been studied between 298 and 4.2°K (pythiaz = 2,4-bis(2-pyridyl)thiazole). At 298°K compound I shows a doublet with ΔEQ(5T2) = 1.29 mm sec?1 and δ1S(5T2) = +0.93 mm sec?1 characteristic of a 5T2 ground state. At 236°K, a second doublet, typical for a 1A1 ground state appears. The transition 5T2 å 1A1 progresses as the temperature is lowered but levels off below ≈ 120°K. At 4.2°K, 59% of the intensity is due to the 1A1 state, and ΔEQ(1A1) = 1.59 mm sec?1 and δ1S(1A1) = +0.26 mm sec?1. In an applied magnetic field, Vzz(1A1) < 0 has been determined Similar results have been obtained with compound II.Debye-Waller factors f5T2 and f1A1. were determined from the Mössbauer spectra under the assumption of Curie-Weiss dependence of the magnetism for the 5T2 and constant μeff for the 1A1 ground state. The resulting temperature dependence of f1A1 is highly unusual thus suggesting complicated magnetic behaviour of both ground states in the transition region. Two mechanisms for the nature of the transition are discussed, a “spin-flip” mechanism being the physically more reasonable one. The assumption of a simple Boltzmann distribution (“spin equilibrium”) may be ruled out for the solid but could be encountered in solutions.  相似文献   
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The valence state of Yb in some of its intermetallics, YbNi2Ge2, YbCu2Si2 and YbPd2Si2 has been investigated by LIII(Yb) absorption edges and X-ray pnotoelectron spectra in the 4f and 4d regions. These studies establish the presence of mixed valence in all three systems and illustrate the utility of 4f and 4d spectra in the study of mixed valence in Yb compounds.  相似文献   
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The homocoupling of aryl halides and the heterocoupling of aryl halides with either aryl bromides or arenes bearing an ortho‐lithiation directing group are presented. The use of a Pd catalyst, in combination with t‐BuLi, allows for the rapid and efficient formation of a wide range of polyaromatic compounds in a one pot procedure bypassing the need for the separate preformation of an organometallic coupling partner. These polyaromatic structures are obtained in high yields, in 10 min at room temperature, with minimal waste generation (E‐factors as low as 1.5) and without the need for strict inert conditions, making this process highly efficient and practical in comparison to classical methods. As illustration, several key intermediates of widely used BINOL‐derived structures are readily prepared.  相似文献   
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