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81.
Jean-Paul Quintard Sabine Hauvette-Frey Michel Pereyre 《Journal of organometallic chemistry》1978,159(2):147-164
The metallation of aryl halides with tributylstannyllithium in THF proceeds via at least three different mechanisms whose relative rates depend on the nature of the halogen, the substrate and the experimental conditions. In the case of aryl bromides, a halogenmetal exchange (major process) is competing with a radical mechanism. With aryl chlorides, an arynic process, a halogenmetal exchange and a radical mechanism are involved. Finally, with aryl fluorides, the arynic process is usual, but it may be strongly competed by a radical mechanism whenever suitable experimental conditions are arranged. 相似文献
82.
Malte Sellin Christian Friedmann Maximilian Maylnder Sabine Richert Ingo Krossing 《Chemical science》2022,13(32):9147
To access the hitherto almost unknown class of clustered transition metal carbonyl cations, the trimetal dodecacarbonyls M3(CO)12 (M = Ru, Os) were reacted with the oxidant Ag+[WCA]−, but yielded the silver complexes [Ag{M3(CO)12}2]+[WCA]− (WCA = [Al(ORF)4]−, [F{Al(ORF)3}2]−; RF = –OC(CF3)3). Addition of further diiodine I2 to increase the redox potential led for M = Ru non-specifically to divalent mixed iodo-RuII-carbonyl cations. With [NO]+, even the N–O bond was cleaved and led to the butterfly carbonyl complex cation [Ru4N(CO)13]+ in low yield. Obviously, ionization of M3(CO)12 with retention of its pseudo-binary composition including only M and CO is difficult and the inorganic reagents did react non-innocently. Yet, the radical cation of the commercially available perhalogenated anthracene derivative 9,10-dichlorooctafluoroanthracene (anthraceneHal) is a straightforward accessible innocent deelectronator with a half-wave potential E1/2 of 1.42 V vs. Fc0/+. It deelectronates M3(CO)12 under a CO atmosphere and leads to the structurally characterized cluster salts [M3(CO)14]2+([WCA]−)2 including a linear M3 chain. The structural characterization as well as vibrational and NMR spectroscopies indicate the presence of three electronically independent sets of carbonyl ligands, which almost mimic M(CO)5, free CO and even [M(CO)6]2+ in one and the same cation.Trimeric M3(CO)12 (M = Ru, Os) reacts with typical inorganic oxidants to unwanted side products. Yet, the 9,10-dichlorooctafluoroanthracene radical cation deelectronates these under CO pressure to give the first homotrimetallic [M3(CO)14]2+ salts. 相似文献
83.
Sabine Martin-Seigle Marie-Claude Pélissier Paul J.T. Filippi 《Flow, Turbulence and Combustion》1998,61(1-4):71-83
This paper deals with acoustic radiation by a thin elastic shell, closed by two perfectly rigid discs, immersed in water and
filled with air. The system is driven by an internal acoustic source. The shell has a length L, is clamped along one of its
boundaries and is freely supported along the other boundary.
Using the infinite domain Green's function, the radiated acoustic pressure is modeled by a hybrid layer potential (linear
combination with nonreal coefficient of a simple layer and a double layer). Using Green's tensor of the in vacuo shell operator,
the shell displacement is expressed as the sum of the field generated by the acoustic pressures and that due to boundary sources.
Finally, the Green's function of the interior Neumann problem is used to express the acoustic pressure inside the shell in
terms of the acoustic source and shell normal displacement: this representation fails for any frequency equal to one of the
resonance frequencies of the shell interior.
To overcome this, a light fluid approximation, which is allowed because the inner fluid is a gas, is adopted. Around each
resonance frequency, an inner approximation is defined which matches the classical outer approximation.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
84.
Celik A Roberts GA White JH Chapman SK Turner NJ Flitsch SL 《Chemical communications (Cambridge, England)》2006,(43):4492-4494
Analysis of the substrate specificity of the self-sufficient cytochrome P450 RhF revealed that the enzyme tends to catalyse the dealkylation of substituted alkyl-aryl ethers with shorter alkyl moieties more readily than equivalent compounds with longer alkyl groups. 相似文献
85.
86.
Emmanuel Cadot Bernadette Salignac Sabine Halut Francis Scheresse 《Angewandte Chemie (International ed. in English)》1998,37(5):611-613
The pH-dependent self-condensation of the [Mo 2 S 2 O 2 ] 2+ complex fragment gives the wheellike Mo12 cluster depicted on the right (ball-and-stick model; large balls: S, medium balls: O, small balls: Mo). Applying this synthetic strategy to other starting materials could provide access to other polyoxothiometalates with well-defined cavities. 相似文献
87.
88.
Dr. Anita Bogomilova Michael Günther Gerhard Hägele Sabine Heuermann Ernst Wagner Kolio Troev 《无机化学与普通化学杂志》2011,637(9):1213-1219
First examples of ene diamines with a phosphonate function at the C=C double bond were obtained by the reaction of dialkyl H‐phosphonates with bis(N‐tert‐butyl)‐diimine derived from glyoxal, [1,4‐bis(tert‐butyl)‐1,4‐diaza‐1,3‐butadiene], and isolated as hydrochlorides. Preferentially the cis‐diamine is formed. The new phosphonates are characterized by multinuclear NMR spectroscopy(1H, 13C, 31P). In addition the methyl ester 8a was characterized by 14,15N NMR spectroscopy as well as by several 2D NMR techniques and single‐crystal X‐ray diffraction, unequivocally establishing the ene diamine structure. In the crystal dimers of the cations are formed by P–O ··· H–N hydrogen bonding. 相似文献
89.
Sindbert S Kalinin S Nguyen H Kienzler A Clima L Bannwarth W Appel B Müller S Seidel CA 《Journal of the American Chemical Society》2011,133(8):2463-2480
In Fo?rster resonance energy transfer (FRET) experiments, the donor (D) and acceptor (A) fluorophores are usually attached to the macromolecule of interest via long flexible linkers of up to 15 ? in length. This causes significant uncertainties in quantitative distance measurements and prevents experiments with short distances between the attachment points of the dyes due to possible dye-dye interactions. We present two approaches to overcome the above problems as demonstrated by FRET measurements for a series of dsDNA and dsRNA internally labeled with Alexa488 and Cy5 as D and A dye, respectively. First, we characterize the influence of linker length and flexibility on FRET for different dye linker types (long, intermediate, short) by analyzing fluorescence lifetime and anisotropy decays. For long linkers, we describe a straightforward procedure that allows for very high accuracy of FRET-based structure determination through proper consideration of the position distribution of the dye and of linker dynamics. The position distribution can be quickly calculated with geometric accessible volume (AV) simulations, provided that the local structure of RNA or DNA in the proximity of the dye is known and that the dye diffuses freely in the sterically allowed space. The AV approach provides results similar to molecular dynamics simulations (MD) and is fully consistent with experimental FRET data. In a benchmark study for ds A-RNA, an rmsd value of 1.3 ? is achieved. Considering the case of undefined dye environments or very short DA distances, we introduce short linkers with a propargyl or alkenyl unit for internal labeling of nucleic acids to minimize position uncertainties. Studies by ensemble time correlated single photon counting and single-molecule detection show that the nature of the linker strongly affects the radius of the dye's accessible volume (6-16 ?). For short propargyl linkers, heterogeneous dye environments are observed on the millisecond time scale. A detailed analysis of possible orientation effects (κ(2) problem) indicates that, for short linkers and unknown local environments, additional κ(2)-related uncertainties are clearly outweighed by better defined dye positions. 相似文献
90.
Maurelli S Vishnuvarthan M Chiesa M Berlier G Van Doorslaer S 《Journal of the American Chemical Society》2011,133(19):7340-7343
The incorporation of Ti ions within the framework of aluminophosphate zeotype AlPO-5 and their chemical reactivity is studied by means of CW-EPR, HYSCORE, and UV-vis spectroscopies. Upon reduction, Ti(3+) ions are formed, which exhibit large (31)P hyperfine couplings, providing direct evidence for framework substitution of reducible Ti ions at Al sites. 相似文献