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51.
Dr. Kuppuswamy Arumugam C. Daniel Varnado Jr. Dr. Stephen Sproules Dr. Vincent M. Lynch Prof. Dr. Christopher W. Bielawski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10866-10875
High yielding syntheses of 1‐(ferrocenylmethyl)‐3‐mesitylimidazolium iodide ( 1 ) and 1‐(ferrocenylmethyl)‐3‐mesitylimidazol‐2‐ylidene ( 2 ) were developed. Complexation of 2 to [{Ir(cod)Cl}2] (cod=cis,cis‐1,5‐cyclooctadiene) or [Ru(PCy3)Cl2(?CH‐o‐O‐iPrC6H4)] (Cy=cyclohexyl) afforded 3 ([Ir( 2 )(cod)Cl]) and 5 ([Ru( 2 )Cl2(?CH‐o‐O‐iPrC6H4)]), respectively. Complex 4 ([Ir( 2 )(CO)2Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH2Cl2. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron‐donating ability of the N‐heterocyclic carbene ligand (ΔTEP=9 cm?1; TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η5‐C5H4COMe)Cp][BF4] as well as the subsequent reduction of the corresponding product [ 5 ][BF4] with decamethylferrocene (Fc*) each proceeded in greater than 95 % yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [ 5 ][BF4] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [ 5 ][BF4] were found to catalyze the ring‐closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo‐first‐order rate constants (kobs) of 3.1×10?4 and 1.2×10?5 s?1, respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second‐generation N‐heterocyclic carbene that featured a 1′,2′,3′,4′,5′‐ pentamethylferrocenyl moiety ( 10 ) was also prepared and metal complexes containing this ligand were found to undergo iron‐centered oxidations at lower potentials than analogous complexes supported by 2 (0.30–0.36 V vs. 0.56–0.62 V, respectively). Redox switching experiments using [Ru( 10 )Cl2(?CH‐o‐O‐iPrC6H4)] revealed that greater than 94 % of the initial catalytic activity was restored after an oxidation–reduction cycle. 相似文献
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Hülya Gizem Özkan Vanrajsinh Thakor Hong-Gui Xu Galyna Bila Prof. Dr. Rostyslav Bilyy Daria Bida Dr. Martin Böttcher Prof. Dr. Dimitrios Mougiakakos Dr. Rainer Tietze Prof. Dr. Andriy Mokhir 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202104420
Elevated levels of reactive oxygen species (ROS) and deficient mitochondria are two weak points of cancer cells. Their simultaneous targeting is a valid therapeutic strategy to design highly potent anticancer drugs. The remaining challenge is to limit the drug effects to cancer cells without affecting normal ones. We have previously developed three aminoferrocene (AF)-based derivatives, which are activated in the presence of elevated levels of ROS present in cancer cells with formation of electron-rich compounds able to generate ROS and reduce mitochondrial membrane potential (MMP). All of them exhibit important drawbacks including either low efficacy or high unspecific toxicity that prevents their application in vivo up to date. Herein we describe unusual AF-derivatives lacking these drawbacks. These compounds act via an alternative mechanism: they are chemically stable in the presence of ROS, generate mitochondrial ROS in cancer cells, but not normal cells and exhibit anticancer effect in vivo. 相似文献
53.
Back Cover: New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures (Chem. Eur. J. 23/2014)
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54.
New Polydentate Trimethylsilyl Chalcogenide Reagents for the Assembly of Polyferrocenyl Architectures
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Mahmood Azizpoor Fard Bahareh Khalili Najafabadi Mahdi Hesari Prof. Dr. Mark S. Workentin Prof. Dr. John F. Corrigan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):7037-7047
A series of polychalcogenotrimethylsilane complexes Ar(CH2ESiMe3)n, (Ar=aryl; E=S, Se; n=2, 3, and 4) can be prepared from the corresponding polyorganobromide and M[ESiMe3] (M=Na, Li). These represent the first examples of the incorporation of such a large number of reactive ?ESiMe3 moieties onto an organic molecular framework. They are shown to be convenient reagents for the preparation of the polyferrocenylseleno‐ and thioesters from ferrocenoyl chloride. The synthesis, structures, and spectroscopic properties of the new silyl chalcogen complexes 1,4‐(Me3SiECH2)2(C6Me4) (E=S, 1 ; E=Se, 2 ), 1,3,5‐(Me3SiECH2)3(C6Me3) (E=S, 3 ; E=Se, 4 ) and 1,2,4,5‐(Me3SiECH2)4(C6H2) (E=S, 5 ; E=Se, 6 ) and the polyferrocenyl chalcogenoesters [1,4‐{FcC(O)ECH2}2(C6Me4)] (E=S, 7 ; E=Se, 8 ), [1,3,5‐{FcC(O)ECH2}3(C6Me3)] (E=S, 9 ; E=Se, 10 ) and [1,2,4,5‐{FcC(O)ECH2}4(C6H2)] (E=S, 11 illustrated; E=Se, 12 ) are reported. The new polysilylated reagents and polyferrocenyl chalcogenoesters have been characterized by multinuclear NMR spectroscopy (1H, 13C, 77Se), electrospray ionization mass spectrometry and, for complexes 1 , 2 , 3 , 4 , 7 , 8 , and 11 , single‐crystal X‐ray diffraction. The cyclic voltammograms of complexes 7 – 11 are presented. 相似文献
55.
本文主要介绍了一系列基于二茂铁骨架的三齿配体:f-amphox、f-ampha、f-amphol和f-amphamide的合成及其应用。这四类手性膦氮配体的铱络合物可以高活性(TON高达1 000 000)、高转化率(>99%)、高对映选择性(>99% ee)地催化(官能团化)酮等底物的不对称氢化反应。该系列配体成功地应用于地诺帕明、苯福林和沙丁胺醇等手性医药中间体的不对称合成。与传统路线相比,这些合成方法更高效,副产物更少,“三废”排放量更低。 相似文献
56.
Guangmei Cai Lihua Zeng Lanqi He Shujian Sun Yexiang Tong Jianyong Zhang 《化学:亚洲杂志》2020,15(13):1963-1969
A series of porphyrin‐based imine gels have been synthesized via dynamic covalent gelation between 5,10,15,20‐tetra(4‐aminophenyl)‐21H,23H‐porphyrin (H2TAPP) derivatives and various aldehyde compounds. The porphyrin‐ferrocene imine gels based on MTAPP (M=H2, Ni2+, Co2+, Pd2+ and Zn2+) and ferrocene‐1,1′‐dicarbaldehyde (NA) display efficient HER, OER and ORR activities in alkaline media. Among the gels, CoTAPP‐NA shows an HER current density of 10 mA cm?2 at low overpotential of 470 mV and small Tafel slope of 110 mV decade?1 in alkaline media. CoTAPP‐NA also exhibits OER catalytic activity with low overpotential (416 mV for 10 mA cm?2). CoTAPP‐NA shows ability in overall water splitting in alkaline media. In addition, CoTAPP‐NA exhibits onset potential (Ep) of 0.95 V and half‐wave potential (E1/2) of 0.84 V in 1.0 mol L?1 KOH solution for oxygen reduction. Moreover, the gel catalyst shows good stability. 相似文献
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