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Dr. Wolfgang Baumann Dr. Dirk Michalik Fabian Reiß Prof. Dr. Axel Schulz Dr. Alexander Villinger 《Angewandte Chemie (International ed. in English)》2014,53(12):3250-3253
Following our interest in nitrogen chemistry, we now describe the synthesis, structure, and bonding of labile disilylated diazene, its GaCl3 adduct, and the intriguing trisilylated diazenium ion [(Me3Si)2N?N‐SiMe3]+, a dark blue and highly labile (Tdecomp>?30 °C) homoleptic cation of the type [R3N2]+. Although direct silylation of Me3Si‐N?N‐SiMe3 failed, the [(Me3Si)2N?N‐SiMe3]+ ion was generated in a straightforward two‐electron oxidation reaction from mercury(II) dihydrazide and Ag[GaCl4]. Moreover, previous structure data of Me3Si‐N?N‐SiMe3 were revised on the basis of new data. 相似文献
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Isolation and Structure of Germylene‐Germyliumylidenes Stabilized by N‐Heterocyclic Imines 下载免费PDF全文
MSc. Tatsumi Ochiai Dr. Tibor Szilvási Dr. Daniel Franz Dr. Elisabeth Irran Prof. Dr. Shigeyoshi Inoue 《Angewandte Chemie (International ed. in English)》2016,55(38):11619-11624
The ditopic germanium complex FGe(NIPr)2Ge[BF4] ( 3 [BF4]; IPr=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) is prepared by the reaction of the amino(imino)germylene (Me3Si)2NGeNIPr ( 1 ) with BF3?OEt2. This monocation is converted into the germylene‐germyliumylidene 3 [BArF4] [ArF=3,5‐(CF3)2‐C6H3] by treatment with Na[BArF4]. The tetrafluoroborate salt 3 [BF4] reacts with 2 equivalents of Me3SiOTf to give the novel complex (OTf)(GeNIPr)2[OTf] ( 4 [OTf]), which affords 4 [BArF4] and 4 [Al(ORF)4] [RF=C(CF3)3] after anion exchange with Na[BArF4] or Ag[Al(ORF)4], respectively. The computational, as well as crystallographic study, reveals that 4 + has significant bis(germyliumylidene) dication character. 相似文献
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Jörg Stierstorfer Dr. Karina R. Tarantik Dipl.‐Chem. Thomas M. Klapötke Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(23):5775-5792
A new way to make a bang : Several functionalized 1‐ethyl‐5‐aminotetrazoles, 1‐ethyl‐5‐nitrimino‐tetrazoles, and copper complexes have been synthesized and their chemical and energetic properties have been comprehensively characterized. The compounds belong to all classes of “energetic materials”: explosives, propellants, and pyrotechnics.
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Dr. Masato Kuratsu Dr. Shuichi Suzuki Dr. Masatoshi Kozaki Dr. Daisuke Shiomi Prof. Kazunobu Sato Prof. Takeji Takui Dr. Tsuneki Kanzawa Prof. Yuko Hosokoshi Dr. Xiao‐Zheng Lan Dr. Yuji Miyazaki Prof. Akira Inaba Prof. Keiji Okada 《化学:亚洲杂志》2012,7(7):1604-1609
The synthesis and the solid state magnetic properties of (nitronyl nitroxide)‐substituted trioxytriphenylamine radical cation tetrachlorogallate, NNTOT+·GaCl4? , are reported. In the temperature region between 300 and 3 K, the magnetic behavior is characterized by the strong intramolecular ferromagnetic interaction (J/kB=+400 K) between the radical ( NN ) and the radical cation ( TOT +) and the weak intermolecular antiferromagnetic interaction (J/kB=?1.9 K) between NNTOT+ ions. Below 3 K, a 3D‐type long‐range magnetic ordering into a weak ferromagnet was observed (TN=2.65 K). The magnetic entropy (Smag=8.97 J K?1 mol?1) obtained by the heat capacity measurement is in good agreement with the theoretical value of R ln3=9.13 J K?1 mol?1 based on the S=1 state. 相似文献
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Tatsumi Ochiai Dr. Daniel Franz Dr. Elisabeth Irran Prof. Dr. Shigeyoshi Inoue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6704-6707
The novel amino(imino)stannylene 1 was prepared by conversion of HNIPr (NIPr=bis(2,6‐diisopropylphenyl)imidazolin‐2‐imino) with one equivalent of Lappert’s tin reagent (Sn[N(SiMe3)2]2). Treatment of 1 with DMAP (4‐dimethylaminopyridine) yields its Lewis acid–base adduct 2 . The reaction of 1 with one equivalent of trimethylsilyl azide results in replacement of the amino group at the tin center by an N3 substituent with concomitant elimination of N(SiMe3)3 to afford dimeric [N3SnNIPr]2 ( 3 ). Remarkably, the reaction of 1 with B(C6F5)3 produces the novel tin(II) monocation 4 +[MeB(C6F5)3]? comprising a four‐membered stannacycle through methyl‐abstraction from the trimethylsilyl group. 相似文献
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Dr. Kai‐Oliver Feldmann Dr. Thomas Wiegand Dr. Jinjun Ren Prof. Dr. Hellmut Eckert Joachim Breternitz Matthias F. Groh Ulrike Müller Prof. Dr. Michael Ruck Dr. Boris Maryasin Prof. Dr. Christian Ochsenfeld Dr. Oliver Schön Prof. Dr. Konstantin Karaghiosoff Prof. Dr. Jan J. Weigand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9697-9712
Although a fairly large number of binary group 15/16 element cations have been reported, no example involving phosphorus in combination with a group 16 element has been synthesized and characterized to date. In this contribution is reported the synthesis and structural characterization of the first example of such a cation, namely a nortricyclane‐type [P3Se4]+. This cation has been independently discovered by three groups through three different synthetic routes, as described herein. The molecular and electronic structure of the [P3Se4]+ cage and its crystal properties in the solid state have been characterized comprehensively by using X‐ray diffraction, Raman, and nuclear magnetic resonance spectroscopies, as well as quantum chemical calculations. 相似文献
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T. O. Petersen E. Tausch Dr. J. Schaefer Dr. H. Scherer Prof.Dr. P. W. Roesky Prof.Dr. I. Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13696-13702
Ion‐like ethylzinc(II) compounds with weakly coordinating aluminates [Al(ORF)4]? and [(RFO)3Al‐F‐Al(ORF)3]? (RF=C(CF3)3) were synthesized in a one‐pot reaction and fully characterized by single‐crystal X‐ray diffraction, NMR and vibrational spectroscopy, and by quantum chemical calculations. The catalytic activity of ion‐like Et‐Zn[Al(ORF)4] in intermolecular hydroamination and in the unusual double hydroamination of anilines and alkynes was investigated. Favorable performance was also found in comparison to the Et2Zn/ [PhNMe2H]+[B(C6F5)4]? system generated in situ at lower catalyst loadings of 2.5 mol %. 相似文献
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Nolan M. Gallagher Hong‐Zhou Ye Shuting Feng Jeffrey Lopez Yun Guang Zhu Troy Van Voorhis Yang Shao‐Horn Jeremiah A. Johnson 《Angewandte Chemie (International ed. in English)》2020,59(10):3952-3955
We present the discovery of a novel radical cation formed through one‐electron oxidation of an N‐heterocyclic carbene–carbodiimide (NHC–CDI) zwitterionic adduct. This compound possesses a distonic electronic structure (spatially separate spin and charge regions) and displays persistence under ambient conditions. We demonstrate its application in a redox‐flow battery exhibiting minimal voltage hysteresis, a flat voltage plateau, high Coulombic efficiency, and no performance decay for at least 100 cycles. The chemical tunability of NHCs and CDIs suggests that this approach could provide a general entry to redox‐active NHC–CDI adducts and their persistent radical ions for various applications. 相似文献
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Richard Betz Moritz M. Reichvilser Emanuel Schumi Christian Miller Peter Klüfers Prof. Dr. 《无机化学与普通化学杂志》2009,635(8):1204-1208
Two phenyl‐substituted λ5‐arsanes were prepared from phenylarsonic acid in two‐step procedures. Their molecular structures were determined by single‐crystal X‐ray diffraction. NBO analyses for the title compounds were conducted. 相似文献
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(5,6‐Dihydro‐1,4‐dithiin‐2‐yl)methanol as a Versatile Allyl‐Cation Equivalent in (3+2) Cycloaddition Reactions 下载免费PDF全文
Jan Hullaert Prof. Dr. Johan M. Winne 《Angewandte Chemie (International ed. in English)》2016,55(42):13254-13258
The title heterocyclic alcohol readily generates a sulfur‐substituted allylic cation upon simple treatment with a protic acid, thus facilitating a synthetically useful stepwise (3+2) cycloaddition reaction pathway with a range of conjugated‐olefin‐type substrates. The introduction of an allyl fragment in this way provided rapid access to a variety of cyclopentanoid scaffolds. The cyclic nature of the cation precursor alcohol was shown to be instrumental for efficient cycloaddition reactions to take place, thus indicating an attractive strategy for controlling the reactivity of heteroatom‐substituted allyl cations. The formal cycloaddition reaction is highly regio‐ and stereoselective and was also used for a short total synthesis of the natural product cuparene in racemic form through a cycloaddition–hydrodesulfurization sequence. 相似文献
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Product‐Derived Bimetallic Palladium Complex Catalyzes Direct Carbonylation of Sulfonylazides 下载免费PDF全文
Jin Zhao Zongyang Li Shaole Song Prof. Dr. Ming‐An Wang Prof. Dr. Bin Fu Prof. Dr. Zhenhua Zhang 《Angewandte Chemie (International ed. in English)》2016,55(18):5545-5549
A novel product‐derived bimetallic palladium complex catalyzes a sulfonylazide‐transfer reaction with the σ‐donor/π‐acceptor ligand CO, and is advantageous given its broad substrate scope, high efficiency, and mild reaction conditions (atmospheric pressure of CO at room temperature). This methodology provides a new approach to sulfonylureas, which are present in both pharmaceuticals and agrochemicals. The synthesis of Glibenclamide on a gram scale further revealed the practical utility of this procedure. Mechanistically, the generation of a bridged bimetallic palladium species derived from the product sulfonylurea is disclosed as the crucial step for this catalytic cycle. 相似文献
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Marius A. Wünsche Tim Witteler Dr. Fabian Dielmann 《Angewandte Chemie (International ed. in English)》2018,57(24):7234-7239
Oxophosphonium ions (R2P=O)+ are fascinating chemical intermediates related to the well‐known acylium cations (RC=O)+, and comprise a tricoordinate phosphorus(V) center with a phosphorus–oxygen double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin‐2‐imine and imidazolin‐2‐olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored. 相似文献
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Ngoc Quang Do Prof. Dr. Anh Tuân Phan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(46):14752-14759
Guanine‐rich sequence motifs, which contain tracts of three consecutive guanines connected by single non‐guanine nucleotides, are abundant in the human genome and can form a robust G‐quadruplex structure with high stability. Herein, by using NMR spectroscopy, we investigate the equilibrium between monomeric and 5′–5′ stacked dimeric propeller‐type G‐quadruplexes that are formed by DNA sequences containing GGGT motifs. We show that the monomer–dimer equilibrium depends on a number of parameters, including the DNA concentration, DNA flanking sequences, the concentration and type of cations, and the temperature. We report on the high‐definition structure of a simple monomeric G‐quadruplex containing three single‐residue loops, which could serve as a reference for propeller‐type G‐quadruplex structures in solution. 相似文献
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Richard Betz Maximilian Pfister Moritz M. Reichvilser Peter Klüfers 《无机化学与普通化学杂志》2008,634(8):1393-1396
The symmetric spiro‐selenurane derived from ethylene glycol, 1,4,6,9‐tetraoxa‐5λ4‐selena‐spiro[4.4]nonane, was prepared from selenium tetrachloride and ethylene glycol and its molecular structure was determined by single crystal X‐ray diffraction. NBO analyses for the title compound and a related compound were conducted to assess the role of the stereochemical active lone pair on the selenium atom on the structure. 相似文献