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31.
32.
A degradable atom transfer radical polymerization inimer: Synthesis,polymerization, and cleavage of the resulting polymer products
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Marios Elladiou Costas S. Patrickios 《Journal of polymer science. Part A, Polymer chemistry》2017,55(17):2831-2839
A novel degradable inimer for atom transfer radical polymerization (ATRP), 2‐(6‐(2‐((2‐bromo‐2‐methylpropanoyl)oxy)ethyl)pyridin‐2‐yl)ethyl methacrylate (PyDEBrMΑ), was synthesized by the two‐step esterification of 2,6‐pyridinediethanol, first with α‐bromoisobutyryl bromide in order to introduce the initiator moiety, and then with methacryloyl chloride in order to introduce the monomer moiety. PyDEBrMA was subsequently used to initiate the self‐condensing ATRP of methyl methacrylate (MMA) to obtain a hyperbranched MMA homopolymer which could be cleaved at the PyDEBrMA residue either by treatment under mildly alkaline hydrolysis conditions (sodium deuteroxide in d6‐DMSO at room temperature) or thermolysis at 150 °C. The lability of the PyDEBrMA residue arises from the presence in its structure of two 2‐(pyridin‐2‐yl)ethyl ester moieties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2831–2839 相似文献
33.
Sergei V. Kostjuk Hui Yee Yeong Brigitte Voit 《Journal of polymer science. Part A, Polymer chemistry》2013,51(3):471-486
This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
34.
Angela Milinkovic Dr. Antoine Dupé Ao. Univ.-Prof. Dr. Ferdinand Belaj Univ.-Prof. Dr. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(55):e202201867
Molybdenum(VI) bis(imido) complexes [Mo(NtBu)2(LR)2] (R=H 1 a ; R=CF3 1 b ) combined with B(C6F5)3 ( 1 a /B(C6F5)3, 1 b /B(C6F5)3) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H2 and Et3SiH affords ion pairs [Mo(NtBu)(NHtBu)(LR)2][HB(C6F5)3] (R=H 2 a ; R=CF3 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H2O leads to [Mo(NtBu)(NHtBu)(LR)2][(HO)B(C6F5)3] (R=H 3 a ; R=CF3 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C6F5)3]−. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(LR)2][{PhCH2O}B(C6F5)3] (R=H 4 a ; R=CF3 4 b ). Catalysis occurs at [HB(C6F5)3]− while [Mo(NtBu)(NHtBu)(LR)2]+ (R=H or CF3) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC). 相似文献
35.
Antoine Barthélemy Dr. Harald Scherer Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(53):e202201369
The tetracationic, univalent cluster compounds [{M(dmpe)}4]4+ (M=Ga, In; dmpe=bis(dimethylphosphino)ethane) were synthesized as their pf salts ([pf]−=[Al(ORF)4]−; RF=C(CF3)3). The four-membered ring in [{M(dmpe)}4]4+ is slightly puckered for M=Ga and almost square planar for M=In. Yet, although structurally similar, only the gallium cluster is prevalent in solution, while the indium cluster forms temperature dependent equilibria that include even the monomeric cation [In(dmpe)]+. This system is the first report of one and the same ligand inducing formation of isoelectronic and isostructural gallium/indium cluster cations. The system allows to study systematically analogies and differences with thermodynamic considerations and bonding analyses, but also to outline perspectives for bond activation using cationic, subvalent group 13 clusters. 相似文献
36.
Kim Glootz Antoine Barthlemy Ingo Krossing 《Angewandte Chemie (International ed. in English)》2021,60(1):208-211
The earth‐metal olefin complex [Ga I (COD)2]+[Al(ORF)4]? (COD=1,5‐cyclooctadiene; RF=C(CF3)3) constitutes the first homoleptic olefin complex of any main‐group metal accessible as a bulk compound. It is straight forward to prepare in good yield and constitutes an olefin complex of a main‐group metal that—similar to many transition‐metals—may adopt the +1 and +3 oxidation states opening potential applications. Crystallographic‐, vibrational‐ and computational investigations give an insight to the atypical bonding between an olefin and a main‐group metal. They are compared to classical transition‐metal relatives. 相似文献
37.
Harry Biller Swantje Lerch Katharina Tölke Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(53):13325-13329
We synthesized new imidazolium-based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2F5)4]−. Phenyl and phenyl derivatives (2-Me, 4-OMe, 2,4-F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C2F5)4] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2-Me-substituted gallate-TAAILs slowly decompose over several weeks, whereas all other gallate-TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66–162 cP, the gallate-TAAILs are promising candidates as electrolytes in electrochemical applications. 相似文献
38.
Dipl.‐Chem. Alexander Rupp Dr. Nataliya Roznyatovskaya Dr. Harald Scherer Dr. Witali Beichel Petra Klose Carola Sturm Dr. Anke Hoffmann Dr. Jens Tübke Prof. Dr. Thorsten Koslowski Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9794-9804
Several, partly new, ionic liquids (ILs) containing imidazolium and ammonium cations as well as the medium‐sized [NTf2]? (0.230 nm3; Tf=CF3SO3?) and the large [Al(hfip)4]? (0.581 nm3; hfip=OC(H)(CF3)2) anions were synthesized and characterized. Their temperature‐dependent viscosities and conductivities between 25 and 80 °C showed typical Vogel–Fulcher–Tammann (VFT) behavior. Ion‐specific self‐diffusion constants were measured at room temperature by pulsed‐gradient stimulated‐echo (PGSTE) NMR experiments. In general, self‐diffusion constants of both cations and anions in [Al(hfip)4]?‐based ILs were higher than in [NTf2]?‐based ILs. Ionicities were calculated from self‐diffusion constants and measured bulk conductivities, and showed that [Al(hfip)4]?‐based ILs yield higher ionicities than their [NTf2]? analogues, the former of which reach values of virtually 100 % in some cases.From these observations it was concluded that [Al(hfip)4]?‐based ILs come close to systems without any interactions, and this hypothesis is underlined with a Hirshfeld analysis. Additionally, a robust, modified Marcus theory quantitatively accounted for the differences between the two anions and yielded a minimum of the activation energy for ion movement at an anion diameter of slightly greater than 1 nm, which fits almost perfectly the size of [Al(hfip)4]?. Shallow Coulomb potential wells are responsible for the high mobility of ILs with such anions. 相似文献
39.
Lisa A. Bischoff Jarno Riefer Raphael Wirthensohn Tobias Bischof Rüdiger Bertermann Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13615-13620
Salts of the tetrakis(pentafluoroethyl)aluminate anion [Al(C2F5)4]− were obtained from AlCl3 and LiC2F5. They were isolated with different counter-cations and characterized by NMR and vibrational spectroscopy and mass spectrometry. Degradation of the [Al(C2F5)4]− ion was found to proceed via 1,2-fluorine shifts and stepwise loss of CF(CF3) under formation of [(C2F5)4−nAlFn]− (n=1–4) as assessed by NMR spectroscopy and mass spectrometry and supported by results of DFT calculations. In addition, the [(C2F5)AlF3]− ion was structurally characterized. 相似文献
40.
本文研究了基于拟相对内部的非凸集值优化问题弱有效元的最优性条件.首先,讨论了弱有效元与线性子空间之间的关系,利用涉及拟相对内部的凸集分离定理,获得了弱有效元的最优性条件.其次,给出了基于拟相对内部弱有效元的Lagrange乘子定理. 相似文献