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91.
Jonathan Mai Michael Morasch Dr. Dawid Jędrzkiewicz Dr. Jens Langer Dr. Bastian Rösch Prof. Dr. Sjoerd Harder 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(3):e202212463
Complex [(DIPePBDI)Ca]2(C6H6), with a C6H62− dianion bridging two Ca2+ ions, reacts with benzene to yield [(DIPePBDI)Ca]2(biphenyl) with a bridging biphenyl2− dianion (DIPePBDI=HC[C(Me)N-DIPeP]2; DIPeP=2,6-CH(Et)2-phenyl). The biphenyl complex was also prepared by reacting [(DIPePBDI)Ca]2(C6H6) with biphenyl or by reduction of [(DIPePBDI)CaI]2 with KC8 in presence of biphenyl. Benzene-benzene coupling was also observed when the deep purple product of ball-milling [(DIPPBDI)CaI(THF)]2 with K/KI was extracted with benzene (DIPP=2,6-CH(Me)2-phenyl) giving crystalline [(DIPPBDI)Ca(THF)]2(biphenyl) (52 % yield). Reduction of [(DIPePBDI)SrI]2 with KC8 gave highly labile [(DIPePBDI)Sr]2(C6H6) as a black powder (61 % yield) which reacts rapidly and selectively with benzene to [(DIPePBDI)Sr]2(biphenyl). DFT calculations show that the most likely route for biphenyl formation is a pathway in which the C6H62− dianion attacks neutral benzene. This is facilitated by metal-benzene coordination. 相似文献
92.
1,3-Dipolar cycloaddition of nitrile oxides, generated from nitroethanol and nitroacetaldehyde derivatives 3, 21 and 22, respectively, and of benzonitrile oxide to 4-vinyldioxolanes 1, 2 gave ca 4:1 erythro/threo mixtures of corresponding isoxazolines. LAH reduction of erytho isoxazolines proceeded with similar (ca 4:1) selectivity to furnish protected ribo-amino-polyols 11, 15,19, DL- and D-lividosamines 31 and 33, respectively, as main products. The DL-lividosamine derivative 33 was obtained pure by crystallization. In the D-series, the corresponding ribo/arabino mixture D-31/D-32 was transformed to the known α-methyl D-lividosaminide D-37. 相似文献
93.
Stephan?HaiberEmail author Xingtao?Ai Henning?Bubert Moritz?Heintze Volker?Brüser Waltraut?Brandl Gabriela?Marginean 《Analytical and bioanalytical chemistry》2003,375(7):875-883
Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions. 相似文献
94.
Volker Seibert Corinna Prohl Ida Schoultz Edward Rhee Rebecca Lopez Kareem Abderazzaq Chunshui Zhou Dieter A Wolf 《BMC biochemistry》2002,3(1):22-15
Background
SCF ubiquitin ligases share the core subunits cullin 1, SKP1, and HRT1/RBX1/ROC1, which associate with different F-box proteins. F-box proteins bind substrates following their phosphorylation upon stimulation of various signaling pathways. Ubiquitin-mediated destruction of the fission yeast cyclin-dependent kinase inhibitor Rum1p depends on two heterooligomerizing F-box proteins, Pop1p and Pop2p. Both proteins interact with the cullin Pcu1p when overexpressed, but it is unknown whether this reflects their co-assembly into bona fide SCF complexes. 相似文献95.
Saalfrank RW Reimann U Göritz M Hampel F Scheurer A Heinemann FW Büschel M Daub J Schünemann V Trautwein AX 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(16):3614-3619
Starting from closely related metal-ligand combinations, completely different oligomeric metal clusters are synthesized. Whereas, picoline-tetrazolylamide HL(1) (1) and zinc or nickel acetate afforded [2x2] grids [M(4)(L(1))(8)] (2), slightly different N-(2-methylthiazole-5-yl)-thiazole-2-carboxamide HL(2) (5 a) and nickel acetate yielded the monometallic complex [Ni(L(2))(2)(OH(2))(2)] (6). In contrast, reaction of 5 a with zinc acetate produced the tetrametallic zinc cluster [Zn(4)O(L(2))(4)(OAc)(2)] (7). Even more surprising, when 3-methyl-substituted HL(3) (5 b) instead of 2-methyl-substituted HL(2) (5 a) was allowed to react under identical conditions with zinc acetate, the cluster [Zn(4)O(L(3))(4)Cl(2)] (8) crystallized from dichloromethane. Clusters 7 and 8 are isostructural. As for 7, in 8 two of the edges of the tetrahedron of zinc ions are doubly bridged, two are singly bridged, and the other two are nonbridged. On the other hand, when iron(II) acetate under aerobic conditions was allowed to react with 5 a, the unprecedented complex [[Fe(3)O(L(2))(2)(OAc)(4)](2)O] (9) was isolated. Cluster 9 is composed of two trimetallic, triangular mu(3)-O(2-)-centered [Fe(3)O(L(2))(2)(OAc)(4)](+) modules, linked by an almost linear mu(2)-O(2-) bridge. The M?ssbauer spectrum together with cyclic voltammetric and square-wave voltammetric measurements of 9 are reported, and 6-9 were characterized unequivocally by single-crystal X-ray structure analyses. 相似文献
96.
Mayilmurugan R Harum BN Volpe M Sax AF Palaniandavar M Mösch-Zanetti NC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(2):704-713
The asymmetric molybdenum(VI) dioxo complexes of the bis(phenolate) ligands 1,4‐bis(2‐hydroxybenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐methylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐dimethylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐3,5‐di‐tert‐butylbenzyl)‐1,4‐diazepane, 1,4‐bis(2‐hydroxy‐4‐flurobenzyl)‐1,4‐diazepane, and 1,4‐bis(2‐hydroxy‐4‐chlorobenzyl)‐1,4‐diazepane (H2(L1)–H2(L6), respectively) have been isolated and studied as functional models for molybdenum oxotransferase enzymes. These complexes have been characterized as asymmetric complexes of type [MoO2(L)] 1–6 by using NMR spectroscopy, mass spectrometry, elemental analysis, and electrochemical methods. The molecular structures of [MoO2(L)] 1–4 have been successfully determined by single‐crystal X‐ray diffraction analyses, which show them to exhibit a distorted octahedral coordination geometry around molybdenum(VI) in an asymmetrical cis‐β configuration. The Mo? Ooxo bond lengths differ only by ≈0.01 Å. Complexes 1 , 2 , 5 , and 6 exhibit two successive MoVI/MoV (E1/2, ?1.141 to ?1.848 V) and MoV/MoIV (E1/2, ?1.531 to ?2.114 V) redox processes. However, only the MoVI/MoV redox couple was observed for 3 and 4 , suggesting that the subsequent reduction of the molybdenum(V) species is difficult. Complexes 1 , 2 , 5 , and 6 elicit efficient catalytic oxygen‐atom transfer (OAT) from dimethylsulfoxide (DMSO) to PMe3 at 65 °C at a significantly faster rate than the symmetric molybdenum(VI) complexes of the analogous linear bis(phenolate) ligands known so far to exhibit OAT reactions at a higher temperature (130 °C). However, complexes 3 and 4 fail to perform the OAT reaction from DMSO to PMe3 at 65 °C. DFT/B3LYP calculations on the OAT mechanism reveal a strong trans effect. 相似文献
97.
98.
99.
Nicole Harmgarth Phil Liebing Liane Hilfert Volker Lorenz Felix Engelhardt Sabine Busse Frank T. Edelmann 《无机化学与普通化学杂志》2019,645(17):1101-1109
New homoleptic complexes of selected rare‐earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(NtBu)]– [= (L)–] were synthesized and fully characterized. Treatment of in situ‐prepared Li(L) ( 1 ) with anhydrous lanthanide(III) chlorides, LnCl3 (Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La3+ formed the octa‐coordinate DME solvate La(L)3(DME) ( 2 ). Using Ce3+, the octa‐coordinate “ate” complex Li(THF)[Ce(L)4] ( 3 ) was formed. Depending on the crystallization conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li. In the case of the smaller Sc3+ and Ho3+ ions, six‐coordinate homoleptic Sc(L)3 ( 4 ) and Ho(L)3 ( 5 ) were isolated. The title compounds were fully characterized by spectroscopic and analytical methods as well as single‐crystal X‐ray diffraction. With Ln = La and Ce, several by‐products incorporating lithium, chlorine and/or oxygen were also isolated and structurally characterized. 相似文献
100.
The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer. We found that the affinity of the cobaltocenium cation is higher than that of the tropylium cation (4+) and is only 2-3 times less than that of the tetraethylammoniun cation (5+). From the variable temperature 1H NMR spectra of this capsule, the free energy of activation at 298 K (deltaGdouble dagger(298K)) for the reorientation of the hydrogen bonded belt between the two parts of the dimer could be determined by total line shape analysis for the aromatic protons of the calixarene. The value of 14.3 +/- 0.2 kcal mol(-1) for the dimeric capsules of 3+ PF6- is very similar to the free activation energy found for dimeric capsules of 1 with 4+ PF6- and 5+ PF6- in C2D4Cl2. It becomes significantly lower, if PF6- is replaced by BF4-. We also found that ten times more DMSO is needed to disrupt the capsule 1 x 3+ x 1 than the corresponding 1 x 1 dimer containing benzene as guest. This demonstrates again the importance of the cation-pi interactions for the stability of such hydrogen-bonded dimeric capsules. 相似文献