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81.
Carsten Lenczyk Dr. Dipak Kumar Roy Bijoy Ghosh Johannes Schwarzmann Prof. Ashwini K. Phukan Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8585-8589
A series of bis(σ)-borane complexes of Group 6 transition metals were prepared by direct dihydroborane coordination to the metal center. Reaction of [M(CO)3(PCy3)2] and two dihydroboranes [DurBH2] and [(Me3Si)2NBH2] (Dur=2,3,5,6-Me4C6H) yielded bis(σ)-borane complexes fac-[M(CO)3(PCy3){η2-(H2BR)}] (R=Dur; 1 : M=Cr, 2 : M=W; R=N(SiMe3)2; 3 : M=Cr, 4 : M=W). In the case of molybdenum, we have isolated an arene complex ( 5 ) with [DurBH2] in which the Dur group acts as a η6-bound ligand, and with [(Me3Si)2NBH2] a similar bis(σ)-borane complex was isolated, cis,trans-[Mo(CO)2(PCy3)2{η2-(H2BN(SiMe3)2}] ( 6 ), with a different pattern of auxiliary ligands. The complexes were investigated by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and computational methods. Quantum theory of atoms in molecules (QTAIM) calculations demonstrated that the borane complexes may be described as pure bis(σ)-borane complexes rather than elongated or stretched examples given that the calculations do not show the presence of a ring-critical point (RCP) at the ring formed by the interactions of the B−H with metal center. 相似文献
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Thies Dirksmeyer Paul Stahl Dr. Cecilia Vallet Prof. Dr. Shirley Knauer Prof. Dr. Michael Giese Prof. Dr. Carsten Schmuck Dr. Christoph Hirschhäuser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202104618
A transfection vector that can home in on tumors is reported. Whereas previous vectors that allow moderately cell selective gene transfection used larger systems, this small-molecule approach paved the way for precise structure-activity relationship optimization. For this, biotin, which mediates cell selectivity, was combined with the potent DNA-binding motif tetralysine-guanidinocarbonypyrrol via a hydrophilic linker, thus enabling SAR-based optimization. The new vector mediated biotin receptor (BR)-selective transfection of cell lines with different BR expression levels. Computer-based analyses of microscopy images revealed a preference of one order of magnitude for the BR-positive cell lines over the BR-negative controls. 相似文献
83.
Rongji Liu Kecheng Cao Adam H. Clark Peilong Lu Montaha Anjass Johannes Biskupek Ute Kaiser Guangjin Zhang Carsten Streb 《Chemical science》2020,11(4):1043
The top-down fabrication of catalytically active molecular metal oxide anions, or polyoxometalates, is virtually unexplored, although these materials offer unique possibilities, for catalysis, energy conversion and storage. Here, we report a novel top-down route, which enables the scalable synthesis and deposition of sub-nanometer molybdenum-oxo clusters on electrically conductive mesoporous carbon. The new approach uses a unique redox-cycling process to convert crystalline MoIVO2 particles into sub-nanometer molecular molybdenum-oxo clusters with a nuclearity of ∼1–20. The resulting molybdenum-oxo cluster/carbon composite shows outstanding, stable electrocatalytic performance for the oxygen reduction reaction with catalyst characteristics comparable to those of commercial Pt/C. This new material design could give access to a new class of highly reactive polyoxometalate-like metal oxo clusters as high-performance, earth abundant (electro-)catalysts.The top-down synthesis and deposition of polyoxometalate-like clusters on porous carbon is reported together with the high electrocatalytic oxygen reduction reactivity of the composite. 相似文献
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Carsten Thöne Jörg Laube Stefan Jäger 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):641-644
Organometallic tungsten selenido complexes of the type [cpW(CO)3]2Sem; m = 2 (1), 3 (2), 4 (3), can be easily synthesized via insertion of selenium into the alkali-metal tungsten bond of LiWcp(CO)3 in appropriate ratios and subsequent oxidation of the produced W-selenolates with O2/SiO2. In contrast, reactions of K2Se6 with [cpW(CO)3Cl] and 18-crown-6 in DMF lead to a mixture óf [cpW(CO)3]2Se4 (3), the η1 Se-bonded selenocarbamato complex [cpW(CO)3SeC(O)NMe2] (4) and the ionic complex [(18-crown-6)K]+[cpW(Se4)2]? (5). The crystal structures of 3 and 4 together with their 77Se NMR data are presented. 相似文献
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