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261.
Palladium complexes incorporating ligands based on a 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantanyl scaffold were used to catalyze the arylation of ethyl cyanoacetate, malononitrile, and various ketones. The products from these reactions can be elaborated to substituted β-arylethylamines and used in microwave-assisted Pictet-Spengler reactions. The protocol developed is suitable for the synthesis of libraries of substituted isoquinolines. 相似文献
262.
Rhenium-185/187 solid-state nuclear magnetic resonance (SSNMR) experiments using NaReO(4) and NH(4)ReO(4) powders provide unambiguous evidence for the existence of high-order quadrupole-induced effects (HOQIE) in SSNMR spectra. Fine structure, not predicted by second-order perturbation theory, has been observed in the (185/187)Re SSNMR spectrum of NaReO(4) at 11.75 T, where the ratio of the Larmor frequency (ν(0)) to the quadrupole frequency (ν(Q)) is ~2.6. This is the first experimental observation that under static conditions, HOQIE can directly manifest in SSNMR powder patterns as additional fine structure. Using NMR simulation software which includes the quadrupole interaction (QI) exactly, extremely large (185/187)Re nuclear quadrupole coupling constants (C(Q)) are accurately determined. QI parameters are confirmed independently using solid-state (185/187)Re nuclear quadrupole resonance (NQR). We explain the spectral origin of the HOQIE and provide general guidelines that may be used to assess when HOQIE may impact the interpretation of the SSNMR powder pattern of any spin-5/2 nucleus in a large, axially symmetric electric field gradient (EFG). We also quantify the errors incurred when modeling SSNMR spectra for any spin-5/2 nucleus within an axial EFG using second-order perturbation theory. Lastly, we measure rhenium chemical shifts in the solid state for the first time. 相似文献
263.
Dr. Cory M. Widdifield Prof. Gabriella Cavallo Dr. Glenn A. Facey Dr. Tullio Pilati Jingxiang Lin Prof. Pierangelo Metrangolo Prof. Giuseppe Resnati Prof. David L. Bryce 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):11949-11962
Although the understanding of intermolecular interactions, such as hydrogen bonding, is relatively well‐developed, many additional weak interactions work both in tandem and competitively to stabilize a given crystal structure. Due to a wide array of potential applications, a substantial effort has been invested in understanding the halogen bond. Here, we explore the utility of multinuclear (13C, 14/15N, 19F, and 127I) solid‐state magnetic resonance experiments in characterizing the electronic and structural changes which take place upon the formation of five halogen‐bonded co‐crystalline product materials. Single‐crystal X‐ray diffraction (XRD) structures of three novel co‐crystals which exhibit a 1:1 stoichiometry between decamethonium diiodide (i.e., [(CH3)3N+(CH2)10N+(CH3)3][2 I?]) and different para‐dihalogen‐substituted benzene moieties (i.e., p‐C6X2Y4, X=Br, I; Y=H, F) are presented. 13C and 15N NMR experiments carried out on these and related systems validate sample purity, but also serve as indirect probes of the formation of a halogen bond in the co‐crystal complexes in the solid state. Long‐range changes in the electronic environment, which manifest through changes in the electric field gradient (EFG) tensor, are quantitatively measured using 14N NMR spectroscopy, with a systematic decrease in the 14N quadrupolar coupling constant (CQ) observed upon halogen bond formation. Attempts at 127I solid‐state NMR spectroscopy experiments are presented and variable‐temperature 19F NMR experiments are used to distinguish between dynamic and static disorder in selected product materials, which could not be conclusively established using solely XRD. Quantum chemical calculations using the gauge‐including projector augmented‐wave (GIPAW) or relativistic zeroth‐order regular approximation (ZORA) density functional theory (DFT) approaches complement the experimental NMR measurements and provide theoretical corroboration for the changes in NMR parameters observed upon the formation of a halogen bond. 相似文献
264.
Reinarz and Fonken have reported2 that the dibromocarbene adduct (1) of 1-methylcyclohexene, upon reaction with methylllthium at 0° in ether, produced exclusively the bicyclobutanes 2 and 3 in relative yields of 60% and 40%, respectively. We have prepared 1 by the phase-transfer method3 of Makosza and Fedorynski in a yield of 67%, found these previous results to be completely reproducible in our hands, and determined the combined yield of the two products (2 and 3) to be 67% also. Thus, the overall 相似文献
265.
Density Functional Theory has been used to study the activation of different olefin polymerisation catalysts by different activators. The results show that biscyclopentadienyl catalyst systems would act as the best catalysts and the activators of the type [CPh3+][A−] would be the best at activating such systems. The competition between different species present in solution for the vacant active site in the catalyst was studied for the [(1,2Me2Cp)2ZrMe+][B(C6F5)3CH3−] system and the pre‐catalyst and AlMe3 were found to be the compounds most likely to form dormant products in solution. 相似文献
266.
Cory C. Pye 《International journal of quantum chemistry》2000,76(1):62-76
The geometries and vibrational frequencies of Li(H2O), n=4, 5, 6, 8, 18, and LiX(H2O)n, X=F, Cl, Br, I; n=3, 6 are calculated at various levels up to MP2/6‐31+G*. The solution structure and vibrational spectra with noncoordinating counterions are most consistent with our tetracoordinate lithium species. The solution spectra of lithium chloride and bromide solutions are consistent with our predicted spectra of ion pairs. It is shown that, to model the Li X vibrational mode correctly, both the lithium and halogen must be solvated with a sufficient number of waters. © 1999 John Wiley & Sons, Inc. Int J Quant Chem 76: 62–76, 2000 相似文献
267.
268.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献