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61.
Dr. Yile Wu Zhao Zhao Dr. Ting Chen Jingjie Tan Dr. Zheng-Wang Qu Prof. Dr. Stefan Grimme Prof. Dr. Yufen Zhao Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(25):e202200666
The germylene species (CH{(CMe)(2,6-iPr2C6H3N)}2)GePCO 1 is shown to react with the Lewis acids (E(C6F5)3 E=B, Al). Nonetheless, 1 participates in FLP chemistry with electron deficient alkynes or olefins, acting as an intramolecular FLP. In contrast, in the presence of B(C6F5)3 and an electron rich alkyne, 1 behaves as Ge-based nucleophile to effect intermolecular FLP addition to the alkyne. This reactivity demonstrates that the reaction pathway is controlled by the nature of the electrophile and nucleophile generated in solution, as revealed by extensive DFT calculations. 相似文献
62.
Dr. Kristina Sorochkina Dr. Konstantin Chernichenko Prof. Dr. Vladimir V. Zhivonitko Dr. Martin Nieger Prof. Dr. Timo Repo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(61):e202201927
Ortho-phenylene-bridged phosphinoborane (2,6-Cl2Ph)2B-C6H4-PCy2 1 was synthesized in three steps from commercially available starting materials. 1 reacts with H2 or H2O under mild conditions to form corresponding zwitterionic phosphonium borates 1-H2 or 1-H2O . NMR studies revealed both reactions to be remarkably reversible. Thus, when exposed to H2, 1-H2O partially converts to 1-H2 even in the presence of multiple equivalents of water in the solution. The addition of parahydrogen to 1 leads to nuclear spin hyperpolarization both in dry and hydrous solvents, confirming the dissociation of 1-H2O to free 1 . These observations were supported by computational studies indicating that the formation of 1-H2 and 1-H2O from 1 are thermodynamically favored. Unexpectedly, 1-H2O can release molecular hydrogen to form phosphine oxide 1-O . Kinetic, mechanistic, and computational (DFT) studies were used to elucidate the unique “umpolung” water reduction mechanism. 相似文献
63.
Dr. Raphaël Nougué Dr. Shintaro Takahashi Dr. Aymeric Dajnak Dr. Eddy Maerten Dr. Antoine Baceiredo Dr. Nathalie Saffon-Merceron Prof. Vicenç Branchadell Dr. Tsuyoshi Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202037
Several base-stabilized silyliumylidene ions ( 2 and 3 ) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one ( 2-H and 3 a ) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO2 and H2. Moreover, HBPin adduct of 3 a ( 8-C ) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H2 molecules. 相似文献
64.
Damien Mahaut Dr. Aurélien Chardon Loïc Mineur Prof. Guillaume Berionni Prof. Benoît Champagne 《Chemphyschem》2021,22(19):1958-1966
The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9-boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms. 相似文献
65.
Kyle M. McCall Bogdan M. Benin Michael Wörle Thomas Vonderach Detlef Günther Maksym V. Kovalenko 《Helvetica chimica acta》2021,104(1):e2000206
Inorganic, lead-free metal halides are widely sought after following the rise of the halide perovskites as outstanding optoelectronic materials, due to their enhanced stability and reduced toxicity. Herein, we report on the solvothermal synthesis of Rb7Sb3Br16, which exhibits a 0D structure comprised of [SbBr6]3− octahedra and edge-sharing bioctahedra [Sb2Br10]4− dimers that order into layers along the c-axis. This all-inorganic material is air-stable and exhibits weak orange photoluminescence (PL) at room temperature. Low-temperature PL and PL excitation (PLE) measurements reveal the presence of two distinct emission bands that originate from these structural units, with the high-energy emission quenching as temperature rises beyond 150 K. We are also able to obtain Rb7Bi3Br16 and Rb7Bi3I16 which both crystallize in orthorhombic symmetry, with Rb7Bi3Br16 presenting weak low-temperature luminescence while Rb7Bi3I16 is non-luminescent. This work expands the library of emissive inorganic metal halides and provides further evidence for the efficacy of low-dimensional Sb−X luminescent centers based on octahedral and edge-sharing [Sb2X10]4− dimers. 相似文献
66.
We revisit recent results on integrable cases for higher-dimensional generalizations of the 2D pentagram map: short-diagonal, dented, deep-dented, and corrugated versions, and define a universal class of pentagram maps, which are proved to possess projective duality. We show that in many cases the pentagram map cannot be included into integrable flows as a time-one map, and discuss how the corresponding notion of discrete integrability can be extended to include jumps between invariant tori. We also present a numerical evidence that certain generalizations of the integrable 2D pentagram map are non-integrable and present a conjecture for a necessary condition of their discrete integrability. 相似文献
67.
Synthesis and Characterization of Flexible Hydrogel Electrodes for Electrochemical Impedance Measurements of Protective Coatings on Metal Sculptures 下载免费PDF全文
A novel conductive anionic hydrogel was synthesized for use as a solid electrolyte for electrochemical impedance spectroscopy (EIS) characterization of the barrier properties of protective coatings on outdoor metalworks, such as bronze sculptures. The AMPS‐co‐PAA hydrogel was soaked in a variety of aqueous salt solutions and characterized by swelling capacity and conductivity in order to determine the most appropriate gel/liquid electrolyte combination for use on culturally significant objects. K2PIPES‐equilibrated hydrogels were selected as the preferred electrodes for this particular application and were used to measure the impedance of a coated substrate, yielding spectra similar to those from standard liquid cells. 相似文献
68.
Strong ionic interactions in noncovalent complexes between poly(ethylene imine), a cationic electrolyte,and Cibacron Blue,a nucleotide mimic – implications for oligonucleotide vectors 下载免费PDF全文
Ömür Çelikbıçak Bekir Salih Chrys Wesdemiotis 《Journal of mass spectrometry : JMS》2014,49(7):597-607
Cationic polymers can bind DNA to form polyplexes, which are noncovalent complexes used for gene delivery into the targeted cells. For more insight on such biologically relevant systems, the noncovalent complexes between the cationic polymer poly(ethylene imine) (PEI) and the nucleotide mimicking dye Cibacron Blue F3G‐A (CB) were investigated using mass spectrometry methods. Two PEIs of low molecular weight were utilized (Mn ≈ 423 and 600 Da). The different types of CB anions produced by Na+/H+ exchanges on the three sulfonic acid groups of CB and their dehydrated counterparts were responsible for complex formation with PEI. The CB anions underwent noncovalent complex formation with protonated, but not with sodiated PEI. A higher proportion of cyclic oligomers were detected in PEI423 than PEI600, but both architectures formed association products with CB. Tandem mass spectrometry studies revealed a significantly stronger noncovalent interaction between PEI and dehydrated CB than between PEI and intact CB. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
69.
Dr. Liping Cao Dr. Marina Šekutor Dr. Peter Y. Zavalij Prof. Dr. Kata Mlinarić‐Majerski Prof. Dr. Robert Glaser Prof. Dr. Lyle Isaacs 《Angewandte Chemie (International ed. in English)》2014,53(4):988-993
Host?guest complexes between cucurbit[7] (CB[7]) or CB[8] and diamantane diammonium ion guests 3 or 6 were studied by 1H NMR spectroscopy and X‐ray crystallography. 1H NMR competition experiments revealed that CB[7]? 6 is among the tightest monovalent non‐covalent complexes ever reported in water with Ka=7.2×1017 M ?1 in pure D2O and 1.9×1015 M ?1 in D2O buffered with NaO2CCD3 (50 mM ). The crystal structure of CB[7]? 6 allowed us to identify some of the structural features responsible for the ultratight binding, including the distance between the NMe3+ groups of 6 (7.78 Å), which allows it to establish 14 optimal ion‐dipole interactions with CB[7], the complementarity of the convex van der Waals surface contours of 6 with the corresponding concave surfaces of CB[7], desolvation of the C?O portals within the CB[7]? 6 complex, and the co‐linearity of the C7 axis of CB[7] with the N+???N+ line in 6 . This work further blurs the lines of distinction between natural and synthetic receptors. 相似文献
70.
Synthesis,Structure, and Reactivity of Diazene Adducts: Isolation of iso‐Diazene Stabilized as a Borane Adduct 下载免费PDF全文
Dipl.‐Chem. Fabian Reiß Prof. Dr. Axel Schulz Dr. Alexander Villinger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(37):11800-11811
This work describes the synthesis and full characterization of a series of GaCl3 and B(C6F5)3 adducts of diazenes R1?N?N?R2 (R1=R2=Me3Si, Ph; R1=Me3Si, R2=Ph). Trans‐Ph?N?N?Ph forms a stable adduct with GaCl3, whereas no adduct, but instead a frustrated Lewis acid–base pair is formed with B(C6F5)3. The cis‐Ph?N?N?Ph ? B(C6F5)3 adduct could only be isolated when UV light was used, which triggers the isomerization from trans‐ to cis‐Ph?N?N?Ph, which provides more space for the bulky borane. Treatment of trans‐Ph?N?N?SiMe3 with GaCl3 led to the expected trans‐Ph?N?N?SiMe3 ? GaCl3 adduct but the reaction with B(C6F5)3 triggered a 1,2‐Me3Si shift, which resulted in the formation of a highly labile iso‐diazene, Me3Si(Ph)N?N; stabilized as a B(C6F5)3 adduct. Trans‐Me3Si?N?N?SiMe3 forms a labile cis‐Me3Si?N?N?SiMe3 ? B(C6F5)3 adduct, which isomerizes to give the transient iso‐diazene species (Me3Si)2N?N ? B(C6F5)3 upon heating. Both iso‐diazene species insert easily into one B?C bond of B(C6F5)3 to afford hydrazinoboranes. All new compounds were fully characterized by means of X‐ray crystallography, vibrational spectroscopy, CHN analysis, and NMR spectroscopy. All compounds were further investigated by DFT and the bonding situation was assessed by natural bond orbital (NBO) analysis. 相似文献