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Viviana B. Dorn María T. Lockhart Adriana B. Pierini 《Journal of organometallic chemistry》2008,693(14):2458-2462
The reaction of trimethyltinsodium (1) with 1-(diethoxyphosphoryl)oxy-1,3-cyclohexadienes in liquid ammonia under irradiation affords the corresponding 1-trimethylstannylcyclohexadienes. We suggest that these reactions occur by an SRN1 mechanism. On the other hand, 2-(diethoxyphosphoryl)oxy-1,3-cyclohexadiene reacts very slowly towards 1 and the substitution product decomposes under the reaction conditions employed. Thus, structurally similar compounds do not behave in the same way under ET conditions. We suggest that this behavior is mainly due to differences in spin density of their radical anions, which affect their fragmentation rates. Our results are supported by computational calculations. 相似文献
75.
Stille reaction was performed with several halo cis-diol derivatives by reaction with allyltributyltin in the presence of a palladium catalyst forming allyl cis-dihydrodiol derivatives. These couplings were conducted with conventional heating as well as with microwave irradiation. Allylbenzene cis-dihydrodiol was obtained with excellent yield using mild conventional heating. However, if the diol moiety is protected with the isopropylidene group, the expected product is obtained only under microwave irradiation. The unusual reactivity observed for the polyoxygenated derivatives suggests assistance of the free hydroxyls in the catalytic cycle. 相似文献
76.
Design and performance of BOREAS,the beamline for resonant X‐ray absorption and scattering experiments at the ALBA synchrotron light source
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Alessandro Barla Josep Nicolás Daniele Cocco Secundino Manuel Valvidares Javier Herrero-Martín Pierluigi Gargiani Jairo Moldes Claude Ruget Eric Pellegrin Salvador Ferrer 《Journal of synchrotron radiation》2016,23(6):1507-1517
The optical design of the BOREAS beamline operating at the ALBA synchrotron radiation facility is described. BOREAS is dedicated to resonant X‐ray absorption and scattering experiments using soft X‐rays, in an unusually extended photon energy range from 80 to above 4000 eV, and with full polarization control. Its optical scheme includes a fixed‐included‐angle, variable‐line‐spacing grating monochromator and a pair of refocusing mirrors, equipped with benders, in a Kirkpatrick–Baez arrangement. It is equipped with two end‐stations, one for X‐ray magnetic circular dichroism and the other for resonant magnetic scattering. The commissioning results show that the expected beamline performance is achieved both in terms of energy resolution and of photon flux at the sample position. 相似文献
77.
Prof. Dr. Daniel Solé Francesco Mariani Prof. Dr. M.‐Lluïsa Bennasar Dr. Israel Fernández 《Angewandte Chemie (International ed. in English)》2016,55(22):6467-6470
A palladium‐catalyzed carbene insertion into C(sp3)?H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd0 and PdII, is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium‐catalyzed C(sp3)?C(sp3) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp3)?H bond functionalization reaction involves an unprecedented concerted metalation–deprotonation step. 相似文献
78.
The electronic properties of a single layer (SL) of pentacene molecules are investigated by high-resolution UV photoemission and near-edge X-ray absorption spectroscopy in different configurations of the SL, either standing up on an aromatic self-assembled monolayer or planar on a bare Cu(001) substrate. The weakly interacting pentacene molecules in the standing-up SL present a semiconducting character, and the empty states distribution reflects that of gas-phase pentacene, while the planar pentacene-Cu system shows a metallic interface with redistribution of the empty molecular states. The highest-occupied molecular orbital lineshape in the weakly interacting SL shows a double structure, attributed to two nonequivalent molecules in the ordered configuration. 相似文献
79.
M. P. Bccar Varela M. C. Caputo M. B. Ferraro P. Lazzeretti M. C. Mariani D. Rial 《International journal of quantum chemistry》2000,77(3):599-606
As gauge invariance of computed magnetic properties, usually partitioned into diamagnetic and paramagnetic terms, is not achieved within the algebraic approximation, unless ad hoc techniques are adopted, a general variational treatment is analyzed, attempting to minimize the term more difficult to evaluate accurately, i.e., the paramagnetic contribution to magnetic susceptibility, by means of a gauge transformation. It is shown that an absolute minimum in a variational sense cannot be determined a priori. However, a “local” minimum of the paramagnetic contribution to magnetic susceptibility can be arrived at by employing general gauge transformations of polynomial form. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 77: 599–606, 2000 相似文献
80.
Maria C. Mariani William Kubin Peter K. Asante Joe A. Guthrie Osei K. Tweneboah 《Entropy (Basel, Switzerland)》2021,23(11)
In this paper, we have modified the Detrended Fluctuation Analysis (DFA) using the ternary Cantor set. We propose a modification of the DFA algorithm, Cantor DFA (CDFA), which uses the Cantor set theory of base 3 as a scale for segment sizes in the DFA algorithm. An investigation of the phenomena generated from the proof using real-world time series based on the theory of the Cantor set is also conducted. This new approach helps reduce the overestimation problem of the Hurst exponent of DFA by comparing it with its inverse relationship with of the Truncated Lévy Flight (TLF). CDFA is also able to correctly predict the memory behavior of time series. 相似文献