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151.
Florian Ritter Dr. Lukas John Dr. Tobias Schindler Julian P. Schroers Simon Teeuwen Dr. Michael E. Tauchert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(59):13436-13444
The dative Pd→B interaction in a series of RDPBR’ Pd0 and PdII complexes (RDPBR’=(o-PR2C6H4)2BR’, diphosphinoborane) was analyzed using XRD, 11B NMR spectroscopy and NBO/NLMO calculations. The borane acceptor discriminates between the oxidation state PdII and Pd0, stabilizing the latter. Reaction of lithium amides with [(RDPBR’)PdII(4-NO2C6H4)I] chemoselectively yields the C−N coupling product. DFT modelling indicates no significant impact of PdII→B coordination on the inner-sphere reductive elimination rate. 相似文献
152.
Dr. Julian Brunner Britta Maier Rose Rosenberg Sebastian Sturm Prof. Dr. Helmut Cölfen Dr. Elena V. Sturm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(66):15242-15248
Applications in the fields of materials science and nanotechnology increasingly demand monodisperse nanoparticles in size and shape. Up to now, no general purification procedure exists to thoroughly narrow the size and shape distributions of nanoparticles. Here, we show by analytical ultracentrifugation (AUC) as an absolute and quantitative high-resolution method that multiple recrystallizations of nanocrystals to mesocrystals is a very efficient tool to generate nanocrystals with an excellent and so-far unsurpassed size-distribution (PDIc=1.0001) and shape. Similar to the crystallization of molecular building blocks, nonclassical recrystallization removes “colloidal” impurities (i.e., nanoparticles, which are different in shape and size from the majority) by assembling them into a mesocrystal. In the case of nanocrystals, this assembly can be size- and shape-selective, since mesocrystals show both long-range packing ordering and preferable crystallographic orientation of nanocrystals. Besides the generation of highly monodisperse nanoparticles, these findings provide highly relevant insights into the crystallization of mesocrystals. 相似文献
153.
Sattelmeyer KW Tirado-Rives J Jorgensen WL 《The journal of physical chemistry. A》2006,110(50):13551-13559
Extensive testing of the SCC-DFTB method has been performed, permitting direct comparison to data available for NDDO-based semiempirical methods. For 34 diverse isomerizations of neutral molecules containing the elements C, H, N, and O, the mean absolute errors (MAE) for the enthalpy changes are 2.7, 3.2, 5.0, 5.1, and 7.2 kcal/mol from PDDG/PM3, B3LYP/6-31G(d), PM3, SCC-DFTB, and AM1, respectively. A more comprehensive test was then performed by computing heats of formation for 622 neutral, closed-shell H, C, N, and O-containing molecules; the MAE of 5.8 kcal/mol for SCC-DFTB is intermediate between AM1 (6.8 kcal/mol) and PM3 (4.4 kcal/mol) and significantly higher than for PDDG/PM3 (3.2 kcal/mol). Similarly, SCC-DFTB is found to be less accurate for heats of formation of ions and radicals; however, it is more accurate for conformational energetics and intermolecular interaction energies, though none of the methods perform well for hydrogen bonds with strengths under ca. 7 kcal/mol. SCC-DFTB and the NDDO methods all reproduce MP2/cc-pVTZ molecular geometries with average errors for bond lengths, bond angles, and dihedral angles of only ca. 0.01 A, 1.5 degrees , and 3 degrees . Testing was also carried out for sulfur containing molecules; SCC-DFTB currently yields much less accurate heats of formation in this case than the NDDO-based methods due to the over-stabilization of molecules containing an SO bond. 相似文献
154.
Rosa L. Camacho-Mendoza Eliazar Aquino-Torres Julian Cruz-Borbolla Jose G. Alvarado-Rodríguez Oscar Olvera-Neria Jayanthi Narayanan Thangarasu Pandiyan 《Structural chemistry》2014,25(1):115-126
DFT studies of both the Fe4 cluster and the Fe(110) surface interaction with pyrrole, furan, thiophene, and selenophene showed that selenophene forms a stabler adsorbate iron complex than the other heterocyclic molecules; this is consistent with the binding energy data that were calculated between the Fe cluster and the Fe(110) surface with the heterocycles. Furthermore, when the adsorption of the compounds with the iron cluster was analyzed by molecular orbital studies, the orbitals of selenophene overlapped more strongly with the Fe atom than that of the other molecules. In TD-DFT, the π → π* peak observed for the molecules disappeared when they formed complexes, and there appeared a charge transfer band (ligand to metal), thus confirming the coordination of these molecules with the cluster. The data suggest that the chemisorption is an exothermic process. 相似文献
155.
Inside Back Cover: Univalent Gallium Complexes of Simple and ansa‐Arene Ligands: Effects on the Polymerization of Isobutylene (Chem. Eur. J. 1/2015) 下载免费PDF全文
156.
157.
Liane M. Moreau Alexandre Herve Mark D. Straub Dominic R. Russo Rebecca J. Abergel Selim Alayoglu John Arnold Augustin Braun Gauthier J. P. Deblonde Yangdongling Liu Trevor D. Lohrey Daniel T. Olive Yusen Qiao Julian A. Rees David K. Shuh Simon J. Teat Corwin H. Booth Stefan G. Minasian 《Chemical science》2020,11(18):4648
We report the structural properties of ultra-small ThO2 and UO2 nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior. Characterization using electron microscopy and small-angle X-ray scattering indicates that growth of the ThO2 and UO2 NPs was confined by the pores of the COF template, resulting in sub-3 nm particles. X-ray absorption fine structure spectroscopy results indicate that the NPs are best described as ThO2 and UO2 materials with unpassivated surfaces. The surface layers of these particles compensate for high surface energy by exhibiting a broader distribution of Th–O and U–O bond distances despite retaining average bond lengths that are characteristic of bulk ThO2 and UO2. The combined synthesis and physical characterization efforts provide a detailed picture of actinide oxide structure at the nanoscale, which remains highly underexplored compared to transition metal counterparts.ThO2 and UO2 nanoparticles synthesized using a COF-5 template exhibit unpassivated surfaces and provide insight into nanoscale properties of actinides. 相似文献
158.
159.
K. J. Jalkanen Julian D. Gale P. R. Lassen L. Hemmingsen A. Rodarte I. M. Degtyarenko R. M. Nieminen S. Brøgger Christensen M. Knapp-Mohammady S. Suhai 《Theoretical chemistry accounts》2008,119(1-3):177-190
In this work we present the experimental and theoretical vibrational absorption (VA) and the theoretical vibrational circular
dichroism (VCD) spectra for aframodial. In addition, we present the theoretical VA and VCD spectra for the diasteriomers of
aframodial. Aframodial has four chiral centers and hence has 24 = 16 diasteriomers, which occur in eight pairs of enantiomers. In addition to the four chiral centers, there is an additional
chirality due to the helicity of the entire molecule, which we show by presenting 12 configurations of the 5S,8S,9R,10S enantiomer
of aframodial. The VCD spectra for the diasteriomers and the 12 configurations of one enantiomer are shown to be very sensitive
not only to the local stereochemistry at each chiral center, but in addition, to the helicity of the entire molecule. Here
one must be careful in analyzing the signs of the VCD bands due to the ‘non-chiral’ chromophores in the molecule, since one
has two contributions; one due to the inherent chirality at the four chiral centers, and one due to the chirality of the side
chain groups in specific conformers, that is, its helicity. Theoretical simulations for various levels of theory are compared
to the experimental VA recorded to date. The VCD spectra simulations are presented, but no experimental VCD and Raman spectra
have been reported to date, though some preliminary VCD measurements have been made in Stephens’ lab in Los Angeles. The flexible
side chain is proposed to be responsible for the small size of the VCD spectra of this molecule, even though the chiral part
of the molecule is very rigid and has four chiral centers. In addition to VCD and Raman measurements, Raman optical activity
(ROA) measurements would be very enlightening, as in many cases bands which are weak in both the VA and VCD, may be large
in the Raman and/or ROA spectra. The feasibility of using vibrational spectroscopy to monitor biological structure, function
and activity is a worthy goal, but this work shows that a careful theoretical analysis is also required, if one is to fully
utilize and understand the experimental results. The reliability, reproduceability and uniqueness of the vibrational spectroscopic
experiments and the information which can be gained from them is discussed, as well as the details of the computation of VA,
VCD and Raman (and ROA) spectroscopy for molecules of the complexity of aframodial, which have multiple chiral centers and
flexible side chains.
Festschrift in Honor of Philip J. Stephens’ 65th Birthday. 相似文献
160.
Julian R. Osman Joe A. Crayston Allin Pratt David T. Richens 《Journal of Sol-Gel Science and Technology》2008,46(2):126-132
Mixed IrO2–TiO2 oxides were prepared by the sol–gel method by adding an aqueous solution of an iridium(III) acetate precursor [Ir3O(OAc)6 (HOAc)3]OAc, to titanium tetraethoxide in ethanol. By using an acetylacetonate modifier to stabilize the hydrolysed titanium alkoxide
and by omitting a catalyst, gels were produced in all cases. Transmission electron microscopy and EDX analysis confirmed the
high dispersion of iridium in the dried gel material on the nanometre scale. The images also show spherical cage features
up to 20 nm in diameter. High mass losses of the gels in the TGA scans suggested low degrees of hydrolysis of the acetate
precursor, but calcination gave a crystalline, mixed oxide (TixIr1–xO2) solid solution. The precursor is also soluble in ethanol, which provides a slightly modified route to similar materials. 相似文献