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排序方式: 共有6623条查询结果,搜索用时 31 毫秒
1.
Nikita M. Ankudinov Prof. Dr. Yulia V. Nelyubina Prof. Dr. Dmitry S. Perekalin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202200195
Diene rhodium complexes are important catalysts in modern organic synthesis. Herein, we report a new approach to such complexes with the uncommon planar chirality. The synthesis is achieved by face-selective coordination of the prochiral 2,5-disubstituted-1,4-benzoquinones (R2-Q) with rhodium precursors containing the chiral auxiliary ligand S-salicyl-oxazoline (S-Salox). Such coordination leads to the formation of (R,R-R2-Q)Rh(S-Salox) complexes in high yields and with exceptional diastereoselectivity (d. r.>20 : 1). Subsequent replacement of the auxiliary ligand provides various benzoquinone rhodium complexes with retention of the planar chirality. Combined theoretical and experimental studies show that due to their electron-withdrawing nature benzoquinones bind metals stronger than the related 1,4-cyclohexadiene, but weaker than other common diene ligands, such as cyclooctadiene. 相似文献
2.
《Mendeleev Communications》2022,32(4):482-484
Rhodium(III) complexes catalyze the insertion of carbenoids generated from diazo compounds into E?H bonds (E = B, Si, N, but not C), although less efficiently than classical rhodium(II) carboxylates, despite formally higher oxidation state of the metal. 相似文献
3.
Dr. Yolimar Gil Dr. Alejandro Castro-Alvarez Dr. Pablo Fuentealba Prof. Evgenia Spodine Dr. Daniel Aravena 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202200336
Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed. 相似文献
4.
Longbin Xian Dr. Nanlin Zhang Zufu Luo Xiaolin Zhang Chonglin Yuan Prof. Dr. Xiuting Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202201682
The electronic structure of quantum dots (QDs) including band edges and possible trap states is an important physical property for optoelectronic applications. The reliable determination of the energy levels of QDs remains a big challenge. Herein we employ cyclic voltammetry (CV) to determine the energy levels of three types of ZnO QDs with different surface ligands. Coupled with spectroscopic techniques, it is found that the onset potential of the first reductive wave is likely related to the conduction band edges while the first oxidative wave originates from the trap states. The determined specific energy levels in CV further demonstrates that the ZnO QDs without surface ligands mainly have oxygen interstitial defects whilst the ZnO QDs covered with ligands contain oxygen vacancies. The present electrochemical method offers a powerful and effective way to determine the energy levels of wide bandgap ZnO QDs, which will boost their device performance. 相似文献
5.
6.
Joachim Loup Uttam Dhawa Fabio Pesciaioli Joanna Wencel‐Delord Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2019,58(37):12803-12818
Molecular syntheses largely rely on time‐ and labour‐intensive prefunctionalization strategies. In contrast, C?H activation represents an increasingly powerful approach that avoids lengthy syntheses of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, and crop protection, among others. The enantioselective functionalization of omnipresent C?H bonds has emerged as a transformative tool for the step‐ and atom‐economical generation of chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium and rhodium catalysts. Indeed, despite significant achievements, the use of inexpensive and sustainable 3d metals in asymmetric C?H activations is still clearly in its infancy. Herein, we discuss the remarkable recent progress in enantioselective transformations via organometallic C?H activation by 3d base metals up to April 2019. 相似文献
7.
Lewis C. Wilkins Youngmin Kim Elishua D. Litle Franois P. Gabbaï 《Angewandte Chemie (International ed. in English)》2019,58(50):18266-18270
Controlling the reactivity of transition metals using secondary, σ‐accepting ligands is an active area of investigation that is impacting molecular catalysis. Herein we describe the phosphine gold complexes [(o‐Ph2P(C6H4)Acr)AuCl]+ ([ 3 ]+; Acr=9‐N‐methylacridinium) and [(o‐Ph2P(C6H4)Xan)AuCl]+ ([ 4 ]+; Xan=9‐xanthylium) where the electrophilic carbenium moiety is juxtaposed with the metal atom. While only weak interactions occur between the gold atom and the carbenium moiety of these complexes, the more Lewis acidic complex [ 4 ]+ readily reacts with chloride to afford a trivalent phosphine gold dichloride derivative ( 7 ) in which the metal atom is covalently bound to the former carbocationic center. This anion‐induced AuI/AuIII oxidation is accompanied by a conversion of the Lewis acidic carbocationic center in [ 4 ]+ into an X‐type ligand in 7 . We conclude that the carbenium moiety of this complex acts as a latent Z‐type ligand poised to increase the Lewis acidity of the gold center, a notion supported by the carbophilic reactivity of these complexes. 相似文献
8.
Kevin Salzmann Dr. Candela Segarra Prof. Dr. Martin Albrecht 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9017-9021
An exceptionally efficient ruthenium-based catalyst for olefin oxidation has been designed by exploiting N,N′-bis(pyridylidene)oxalamide (bisPYA) as a donor-flexible ligand. The dynamic donor ability of the bisPYA ligand, imparted by variable zwitterionic and neutral resonance structure contributions, paired with the redox activity of ruthenium provided catalytic activity for Lemieux–Johnson-type oxidative cleavage of olefins to efficiently prepare ketones and aldehydes. The ruthenium bisPYA complex significantly outperforms state-of-the-art systems and displays extraordinary catalytic activity in this oxidation, reaching turnover frequencies of 650 000 h−1 and turnover numbers of several millions. 相似文献
9.
Chase A. Salazar Joseph J. Gair Kaylin N. Flesch Ilia A. Guzei Jared C. Lewis Shannon S. Stahl 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):10965-10969
Mono-N-protected amino acids (MPAAs) are increasingly common ligands in Pd-catalyzed C−H functionalization reactions. Previous studies have shown how these ligands accelerate catalytic turnover by facilitating the C−H activation step. Here, it is shown that MPAA ligands exhibit a second property commonly associated with ligand-accelerated catalysis: the ability to support catalytic turnover at substoichiometric ligand-to-metal ratios. This catalytic role of the MPAA ligand is characterized in stoichiometric C−H activation and catalytic C−H functionalization reactions. Palladacycle formation with substrates bearing carboxylate and pyridine directing groups exhibit a 50–100-fold increase in rate when only 0.05 equivalents of MPAA are present relative to PdII. These and other mechanistic data indicate that facile exchange between MPAAs and anionic ligands coordinated to PdII enables a single MPAA to support C−H activation at multiple PdII centers. 相似文献
10.