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排序方式: 共有1103条查询结果,搜索用时 31 毫秒
1.
Reshma Jose Dr. Srinivasu Kancharlapalli Dr. Tapan K. Ghanty Prof. Sourav Pal Prof. Gopalan Rajaraman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202104526
The coordinatively unsaturated chromium(II)-based Cr3[(Cr4Cl)3(BTT)8]2 (Cr−BTT; BTT3−=1,3,5-benzenetristetrazolate) metal–organic framework (MOF) has been shown to exhibit exceptional selectivity towards adsorption of O2 over N2/H2. Using periodic density functional theory (DFT) calculations, we attempted to decipher the origin of this puzzling selectivity. By computing and analyzing the magnetic exchange coupling, binding energies, the partial density of states (pDOS), and adsorption isotherms for the pristine and gas-bound MOFs [(Cr4(X)4Cl)3(BTT)8]3− (X=O2, N2, and H2), we unequivocally established the role of spin states and spin coupling in controlling the gas selectivity. The computed geometries and gas adsorption isotherms are consistent with the earlier experiments. The binding of O2 to the MOF follows an electron-transfer mechanism resulting in a CrIII superoxo species (O2.−) with a very strong antiferromagnetic coupling between the two centers, whereas N2/H2 are found to weakly interact with the metal center and hence only slightly perturb the associated coupling constants. Although the gas-bound and unbound MOFs have an S=0 ground state (GS), the nature of spin the configurations and the associated magnetic exchanges are dramatically different. The binding energy and the number of oxygen molecules that can favorably bind to the Cr center were found to vary with respect to the spin state, with a significant energy margin (47.6 kJ mol−1). This study offers a hitherto unknown strategy of using spin state/spin couplings to control gas adsorption selectivity in MOFs. 相似文献
2.
Simultaneous Induction of Axial and Planar Chirality in Arene–Chromium Complexes by Molybdenum‐Catalyzed Enantioselective Ring‐Closing Metathesis 下载免费PDF全文
Prof.Dr. Ken Kamikawa Dr. Sachie Arae Dr. Wei‐Yi Wu Chihiro Nakamura Prof.Dr. Tamotsu Takahashi Prof.Dr. Masamichi Ogasawara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):4954-4957
The molybdenum‐catalyzed asymmetric ring‐closing metathesis of the various Cs‐symmetric (π‐arene)chromium substrates provides the corresponding bridged planar‐chiral (π‐arene)chromium complexes in excellent yields with up to >99 % ee. With a bulky and unsymmetrical substituent, such as N‐indolyl or 1‐naphthyl, at the 2‐positions of the η6‐1,3‐diisopropenylbenzene ligands, both biaryl‐based axial chirality and π‐arene‐based planar chirality are simultaneously induced in the products. The axial chirality is retained even after the removal of the dicarbonylchromium fragment, and the chiral biaryl/heterobiaryl compounds are obtained with complete retention of the enantiopurity. 相似文献
3.
Chemoselective Chromium(II)‐Catalyzed Cross‐Coupling Reactions of Dichlorinated Heteroaromatics with Functionalized Aryl Grignard Reagents 下载免费PDF全文
Dr. Andreas K. Steib Dr. Olesya M. Kuzmina Sarah Fernandez Dr. Sushant Malhotra Prof. Paul Knochel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1961-1965
Chromium(II) chloride catalyzes the chemoselective cross‐coupling reaction of dichloropyridines with a range of functionalized (hetero)aromatic Grignard reagents at room temperature. Functional groups, such as esters and acetals, are well tolerated in this transformation. Previously challenging substrates, quinolines and isoquinolines, participate in the selective Cr‐catalyzed cross‐coupling in cyclopentyl methyl ether (CPME) as the solvent. The effective purging of Cr salts is demonstrated by using various solid supports. 相似文献
4.
Dr. Morten Gotthold Vinum Laura Voigt Colby Bell Dmytro Mihrin Prof. Dr. René Wugt Larsen Prof. Dr. Kensha Marie Clark Prof. Dr. Kasper S. Pedersen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(10):2143-2147
β-Diketonates, such as acetylacetonate, are amongst the most common bidentate ligands towards elements across the entire periodic table and are considered wholly redox-inactive in their complexes. Herein we show that complexation of 1,1,1,5,5,5-hexafluoroacetylacetonate (hfac−) to CrII spontaneously affords CrIII and a reduced β-diketonate radical ligand scaffold, as evidenced by crystallographic analysis, magnetic measurements, optical spectroscopy, reactivity studies, and DFT calculations. The possibility of harnessing β-diketonates as electron reservoirs opens up possibilities for new metal–ligand concerted reactivity in the ubiquitous β-diketonate coordination chemistry. 相似文献
5.
Dr. Francesco Della Monica Dr. Veronica Paradiso Prof. Dr. Alfonso Grassi Dr. Stefano Milione Prof. Dr. Luigi Cavallo Prof. Dr. Carmine Capacchione 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5347-5353
A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers. 相似文献
6.
Tae Hee Kim Hyun Mo Lee Hee Soo Park Sung Dong Kim Su Jin Kwon Atsushi Tahara Hideo Nagashima Bun Yeoul Lee 《应用有机金属化学》2019,33(4)
The original Sasol catalytic system for ethylene tetramerization is composed of a Cr source, a PNP ligand, and MAO (methylaluminoxane). The use of expensive MAO in excess has been a critical concern in commercial operation. Many efforts have been made to replace MAO with non‐coordinating anions (e.g., [B(C6F5)4]?); however, most of such attempts were unsuccessful. Herein, an extremely active catalytic system that avoids the use of MAO is presented. The successive addition of two equivalent [H(OEt2)2]+[B(C6F5)4]? and one equivalent CrCl3(THF)3 to (acac)AlEt2 and subsequent treatment with a PNP ligand [CH3(CH2)16]2C(H)N(PPh2)2 ( 1 ) yielded a complex presumably formulated as [ 1 ‐CrAl (acac)Cl3(THF)]2+[B(C6F5)4]?2, which exhibited high activity when combined with iBu3Al (1120 kg/g‐Cr/h; ~4 times that of the original Sasol system composed of Cr (acac)3, iPrN(PPh2)2, and MAO). Via the introduction of bulky trialkylsilyl substituents such as –SiMe3, –Si(nBu)3, or –SiMe2(CH2)7CH3 at the para‐position of phenyl groups in 1 (i.e., by using [CH3(CH2)16]2C(H)N[P(C6H4‐p‐SiR3)2]2 instead of 1 ), the activities were dramatically improved, i.e., tripled (2960–3340 kg/g‐Cr/h; more than 10 times that of the original Sasol system). The generation of significantly less PE (<0.2 wt%) even at a high temperature is another advantage achieved by the introduction of bulky trialkylsilyl substituents. NMR studies and DFT calculations suggest that increase of the steric bulkiness on the alkyl‐N and P‐aryl moieties restrict the free rotation around (alkyl)N–P (aryl) bonds, which may cause the generation of more robust active species in higher proportion, leading to extremely high activity along with the generation of a smaller amount of PE. 相似文献
7.
Prof. Dr. Javier A. Cabeza Dr. Pablo García-Álvarez Prof. Dr. Mar Gómez-Gallego Laura González-Álvarez Alba D. Merinero Prof. Dr. Miguel A. Sierra 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8635-8642
The reactivity of amidinatotetrylenes of the type E(tBu2bzm)R1 (E=Si, Ge; tBu2bzm=N,N′-bis(tertbutyl)benzamidinate; R1=alkyl or aryl) with the chromium Fischer alkynylcarbene complexes [Cr{C(OEt)C2R2}(CO)5] (R2=Ph; ferrocenyl, Fc) has been studied. At room temperature, two different reaction pathways have been identified: (a) attack of the amidinatotetrylene to the alkynyl C2 atom (γ-attack), which leads to σ-allenyl complexes in which the original Ccarbene atom maintains its attachment to the Cr(CO)5 and OEt groups (compounds 3 ), and (b) attack of the amidinatotetrylene to the Ccarbene atom (α-attack), which ends in σ-allenyl complexes in which the original Ccarbene atom is not attached to the metal atom and has been inserted into an E−N bond of the amidinatotetrylene forming an E-C-N-C-N five-membered ring (compounds 4 ). It has been found that compounds 3 are thermodynamically less stable than their corresponding 4 isomers and that some of the former (E=Ge; R1=CH2SiMe3) can be transformed into the latter upon heating. At high temperatures (>70 °C) the reactions involving bulky amidinatotetrylenes (R1=Mes, tBu) end in the carbene-substitution products [Cr{E(tBu2bzm)R1}(CO)5]. 相似文献
8.
Colloidal Surface Active Maghemite Nanoparticles for Biologically Safe CrVI Remediation: from Core‐Shell Nanostructures to Pilot Plant Development 下载免费PDF全文
Dr. Massimiliano Magro Dr. Stefania Domeneghetti Davide Baratella Dr. Petr Jakubec Prof. Dr. Gabriella Salviulo Dr. Emanuela Bonaiuto Dr. Paola Venier Ondřej Malina Dr. Jiří Tuček Dr. Václav Ranc Dr. Giorgio Zoppellaro Prof.Dr. Radek Zbořil Prof. Dr. Fabio Vianello 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14219-14226
The present study is aimed at the exploration of achievable improvements for CrVI ex situ and in situ water remediation by using novel naked colloidal maghemite (γ‐Fe2O3) nanoparticles (surface active maghemite nanoparticles, SAMNs). The reliability of SAMNs for CrVI binding and removal was demonstrated, and SAMN@CrVI complex was characterized, as well as the covalent nature of the absorption was unequivocally proved. SAMNs were structurally and magnetically well conserved after CrVI binding. Thus, in consideration of their affinity for CrVI, SAMNs were exploited in a biological model system, mimicking a real in situ application. The assay evidenced a progressive reduction of revertant colonies of Salmonella typhimurium TA100 strain, as maghemite nanoparticles concentration increased, till the complete suppression of CrVI mutagen effect. Finally, an automatic modular pilot system for continuous magnetic removal and recovery of CrVI from water is proposed. SAMNs, thanks to their colloidal, binding, and catalytic properties, represent a promising tool as a reliable nanomaterial for water remediation by CrVI. 相似文献
9.
Determination of hexavalent chromium in traditional Chinese medicines by high‐performance liquid chromatography with inductively coupled plasma mass spectrometry 下载免费PDF全文
Peng Li Li‐min Li Jing Xia Shuai Cao Xin Hu Hong‐Zhen Lian Shen Ji 《Journal of separation science》2015,38(23):4043-4047
An analytical method that combined high‐performance liquid chromatography with inductively coupled plasma mass spectrometry has been developed for the determination of hexavalent chromium in traditional Chinese medicines. Hexavalent chromium was extracted using the alkaline solution. The parameters such as the concentration of alkaline and the extraction temperature have been optimized to minimize the interconversion between trivalent chromium and hexavalent chromium. The extracted hexavalent chromium was separated on a weak anion exchange column in isocratic mode, followed by inductively coupled plasma mass spectrometry determination. To obtain a better chromatographic resolution and sensitivity, 75 mM NH4NO3 at pH 7 was selected as the mobile phase. The linearity of the proposed method was investigated in the range of 0.2–5.0 μg L?1 (r2 = 0.9999) for hexavalent chromium. The limits of detection and quantitation are 0.1 and 0.3 μg L?1, respectively. The developed method was successfully applied to the determination of hexavalent chromium in Chloriti lapis and Lumbricus with satisfactory recoveries of 95.8–112.8%. 相似文献
10.
Arumugam Thangavel Marika Wieliczko Christopher Scarborough Birger Dittrich John Bacsa 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(11):936-943
In the crystal structure of the title homoleptic CrII complex, [Cr(CH3CN)6](C24H20B)2·CH3CN, the [Cr(CH3CN)6]2+ cation is a high‐spin d4 complex with strong static, rather than dynamic, Jahn–Teller distortion. The electron density of the cation was determined by single‐crystal X‐ray refinements using aspherical structure factors from wavefunction calculations. The detailed picture of the electronic density allowed us to assess the extent and directionality of the Jahn–Teller distortion of the CrII cation away from idealized octahedral symmetry. The topological analysis of the aspherical d‐electron density about the CrII cation showed that there are significant valence charge concentrations along the axial Cr—N axes. Likewise, there were significant valence charge depletions about the CrII cation along the equatorial Cr—N bonds. These charge concentrations are in accordance with a Jahn–Teller‐distorted six‐coordinate complex. 相似文献