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11.
Although very bulky ligands e.g.(o-MeC6H4)3E or (μ-C10H7)3E (E = P or As) are inert, the normal photochemical or thermal reaction of tertiary phosphines or arsines, L, with [Mn2(CO)10] is CO substitution with the formation of [Mn2(CO)8(L)2] derivatives (I). At elevated temperatures some triarylarsines, R3As, undergo Lambert's reaction with ligand fragmentation to give [Mn2(CO)8(μ-AsR2)2] complexes (II) (R = Ph, p-MeOC6H4, p-FC6H4, or p-CIC6H4) even though, in the absence of [Mn2(CO)10] R3As are stable under the same conditions. Exceptional behaviour is exhibited by (p-Me2NC6H4)3- As which forms a product of type I; by some HN(C6H4)2AsR which give a product of type II as a result of loss of the non-aryl groups R = PhCH2, cyclo-C6H11, or MeO; and by Ph(α-C10H72P which is the only phosphine to form a product of type II, albeit in trace amounts only. The thermal decomposition of a n-butanol solution of [Mn2(CO)8(AsPh3)2] in a sealed tube gives C6H6 and [Mn2(CO)8(α-AsPh2)2], whilst in an open system in the presence of various tertiary phosphines, L, [Mn(H)(CO)3(L)2] are obtained. It is suggested that Lambert's reaction is a thermal fragmentation of [Mn(CO)4(AsR3]* radicals, the first to be recognised. They lose the radical R* which abstracts hydrogen from the solvent. The resulting [Mn(CO)4(AsR2)] moiety dimerises to [Mn2(CO)8-(α-AsR2)2]. the reaction is facilitated by the stability of the departing radical (e.g. PhCH2 or MeO) and, as the crowding about As is relieved, by its size (e.g. Ph, cyclo-C6H11, o-MeC6H4, or α-C10H7). In general, phosphine-substituted radicals [Mn(CO)4(PR)3]* do not undergo this decomposition, probably because the PC bonds are much stronger than AsC. 相似文献
12.
Emile Bienvenu Kurt‐Jürgen Hoffmann Michael Ashton Pierre Claver Kayumba 《Biomedical chromatography : BMC》2013,27(11):1554-1559
Owing to heterogeneity in therapeutic response, efavirenz is of research and clinical interest. There is a need to quantitate it using noncostly and selective methods. A method for efavirenz quantitation in plasma containing HIV and tuberculosis drugs was developed. Chromatographic separation was carried out using a C18 column. The mobile phase consisted of 0.1% formic acid and acetonitrile, and was pumped at a flow rate of 0.3 mL/min. Efavirenz and ritonavir (internal standard) were monitored at 247 nm. Plasma proteins were precipitated by centrifugation. The analysis time was 6 min. The response was linear (r = 0.9997). The accuracy ranged between 98 and 115% (intraday) and between 99 and 117% (interday). The precision ranged from 1.670 to 4.087% (intraday) and from 3.447 to 13.347% (interday). Recovery ranged from 98 to 132%. Stability ranged between 99 and 123%. The selectivity was proven by analysis of drugs used for the management of HIV/AIDS and tuberculosis. Plasma sample analysis showed an efavirenz retention time of 5.57 min and a peak plasma concentration of 2.4 µg/mL occurring at 2 h. This method is rapid and selective, and thus suitable for monitoring efavirenz in patients with HIV/AIDS alone or co‐infected with tuberculosis in a less resourced setting. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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A noninterferometric optical fiber add-drop channel filter based on a mismatched twin-core photosensitive-cladding fiber and long-period fiber grating is demonstrated. With assistance from the fiber grating, co-directional spectrally selective cross coupling between the two cores can be realized with an efficiency of 90%. 相似文献
15.
The rational design of a bis(phosphine oxide) host which is capable of binding a benzylic amine is presented. The ability of this host to increase the rate of addition of 4-fluorobenzylamine to N-phenylmaleimide is rationalized in terms of the enhancement of the nucleophilicity of the benzylic amine. 相似文献
16.
Prakash Sista Mahesh P. Bhatt Ashton R. Mccary Hien Nguyen Jing Hao Michael C. Biewer Mihaela C. Stefan 《Journal of polymer science. Part A, Polymer chemistry》2011,49(10):2292-2302
Poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene} ( P1 ) homopolymer and poly{4,8‐bis(4‐decylphenylethynyl)benzo[1,2‐b:4,5‐b′]dithiophene ‐alt‐thiophene} ( P2 ) alternating copolymer have been synthesized by Stille coupling polymerization. The field‐effect mobilities of both polymers were measured on both untreated and silane‐treated OFET devices. Various silanes were selected to allow an incremental increase in the hydrophobicity of the silicon dioxide dielectric. A direct correlation was observed between the hydrophobicity of the silicon dioxide dielectric surface and the enhancement of the field‐effect mobilities. The highest mobilities for both polymers were measured on the OFET devices treated with heptadecafluoro‐1,1,2,2‐tetrahydro‐decyl‐1‐trimethoxysilane (FS) which generated the most hydrophobic surface. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
17.
M. Manickam Alun Smith Maura Belloni Elwyn J. Shelley Peter R. Ashton Neil Spencer Jon A. Preece 《Liquid crystals》2002,29(4):497-504
The synthesis and characterization of four C 60 Bingel cyclopropanation adducts incorporating bis-biphenylene (three adducts) and bis-triphenylene (one adduct) moieties are described. The thermal analysis (POM and DSC) of these materials reveals that they are not liquid crystalline. However, two of the precursor bis-biphenylene malonate esters possess monotropic mesophases. Furthermore, each of the corresponding C 60 adducts is miscible in the melts of the precursor malonate ester, and at low dopings, retains the liquid crystalline monotropic mesophases of the precursor. 相似文献
18.
W. Simarew S. G. Menefee O. R. Overman A. Gorbatschewa H. Chr Jorgensen I. V. Hunt A. Konoplew H. Fincke C. Ehrlich R. Trommsdorff M. Asdrubali S. Hadwen R. Gwatkin F. K. Neave H. D. Kay W. R. Graham R. Aschaffenburg A. Jepsen P. Madelung Ch. Paley H. Kreker A. M. Williams May Davies S. B. Thomas G. M. Phillips W. M. Ashton G. D. Simons J. Davies B. F. Thomas L. Little H. A. Sirks G. Sjöström P. Jaulmes L. Poujol und J. A. B. Smith 《Fresenius' Journal of Analytical Chemistry》1943,126(7):282-286
Ohne Zusammenfassung 相似文献
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We consider the problem of transport in a one-parameter family of piecewise rotations of the torus, for rotation number approaching 1∕4. This is a zero-entropy system which in this limit exhibits a divided phase space, with island chains immersed in a "pseudo-chaotic" region. We identify a novel mechanism for long-range transport, namely the adiabatic destruction of accelerator-mode islands. This process originates from the approximate translational invariance of the phase space and leads to long flights of linear motion, for a significant measure of initial conditions. We show that the asymptotic probability distribution of the flight lengths is determined by the geometric properties of a partition of the accelerator-mode island associated with the flight. We establish the existence of flights travelling distances of order O(1) in phase space. We provide evidence for the existence of a scattering process that connects flights travelling in opposite directions. 相似文献