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81.
M. Jesús Rodríguez M. Isabel Fernndez Ana M. Gonzlez‐Noya Marcelino Maneiro Rosa Pedrido Miguel Vzquez Bruno Donnadieu Manuel R. Bermejo 《无机化学与普通化学杂志》2005,631(11):2161-2166
M(HL)(H2O)n complexes have been obtained by the electrochemical reaction of Fe, Co, Ni, Cu, Zn and Cd anodes with the potentially pentadentate and trianionic asymmetrical Schiff base 3‐aza‐N‐{2‐[1‐aza‐2‐(5‐nitro‐2‐hydroxylphenyl)‐vinyl]phenyl}‐4‐(5‐nitro‐2‐hydroxyphenyl)but‐3‐enamide (H3L), containing a hard amido donor atom. The complexes have been characterized by elemental analysis, mass spectrometry, IR and 1H NMR spectroscopies, magnetic measurements and molar conductivities. Co(HL)(H2O) ( 2 ) has been found to rearrange in DMF solution into a crystallographically solved octahedral complex, CoL1(H2O)2 ( 7 ) [where H2L1 is the symmetrical Schiff base ligand N,N′‐(1,2‐phenylene)‐bis(5‐nitro‐3‐hydroxysalicylidenimine)]. A hydrolysis mechanism is discussed to explain this rearrangement. 相似文献
82.
Polymer-supported O-alkylisoureas were prepared by reaction of an alcohol with a polymer-supported carbodiimide under copper(II) catalysis. These reagents were used to transform carboxylic acids into the corresponding methyl, benzyl, allyl, and p-nitrobenzyl esters in a highly chemoselective manner in high yields and in very high purity after simple resin filtration and solvent evaporation. The reactions could be carried out using both conventional or microwave heating, with reaction times as short as 3-5 min in the latter case, without compromising yield, purity, or chemoselectivity. Unfortunately, the corresponding solid-supported tert-butyl isoureas could not be prepared. 相似文献
83.
Analytic expressions are given for integrals of the Coulomb Green function with Slater type atomic orbitals. The results involve hypergeometric functions.Supported by the National Institutes of Health, Grant No. GM23223. 相似文献
84.
Roland Achini 《Helvetica chimica acta》1981,64(7):2203-2218
The construction of new or novelly functionalized annulated and bridged tricylic compounds by two consecutive C,C-bond formations (a and b in la , Scheme 1) is described. In a first step, chloroalkyl-substituted aminonitriles yielded pyrrolidines 8 , 15a , 15b , 23 , 25 and piperidine 18 by carbanionic ring closure (Schemes 5, 6, 7 and 8). Subsequent Friedel-Crafts cyclization transformed the β-aminonitriles 8 , 15a , 15b , and 18 either directly or via their carboxylic acid derivatives to the indeno [1, 2-c]pyrrole, 2, 5-methano-3-benzazocine, benz [f]isoindoline and 1, 4-ethano-2-benzazapine skeletons 11 , 16a , 16b and 21 , respectively (Schemes 5, 6 and 7). By classical ring expansion reactions the pyrrolo [3, 4-c]isoquinoline and benzopyrano-[3, 4-c]pyrrole skeletons 28 resp. 31 were obtained from 11 (Scheme 9). 相似文献
85.
Alkyl ketene dimer (AKD) sizing of paper involves the redistribution of the wax over the fibre surface upon heating. The two
major mechanisms widely studied so far are the spreading of an autophobic precursor of molten AKD and AKD vapour transport
and re-deposition on the fibre surface. All previous work assumed that the transport of AKD vapour could be expressed by the
change of water contact angle with substrates that were exposed to the vapour. Information regarding the chemical composition
of the vapour phase above the AKD wax has not been found in the literature. In this work, a simple method for analysing the
chemical composition of the vapour is established. Our preliminary results indicated that the chemical composition of AKD
vapour in the temperature range of 75–80 °C is dominantly fatty acids. This suggests that the sizing effect by actual AKD
molecules via the vapour deposition mechanism is likely to be insignificant in this temperature range. This also implies that
fatty acids play a positive role in AKD sizing. The chemical stability of AKD in this temperature range is also studied. 相似文献
86.
Piero Zanello Renato Seeber Bruno Crociani Marino Nicolini 《Transition Metal Chemistry》1980,5(1):45-48
Summary The electrochemical behaviour of a series of cationic platinum(II) isocyanide complexes has been studied in acetonitrile. All the tested compounds are oxidized at a platinum electrode via a two-electron process and reduced at a platinum or mercury electrode via two successive one-electron steps. The anodic step involves the formation of platinum(IV) complexes. The main reduction product formed in correspondence to the first cathodic process is a stable dimer platinum(I) containing bridging isocyanide ligands. Platinum(0) species are formed in the subsequent reduction step. 相似文献
87.
The fluxional molecule Os3(CO)7[P(OMe)3]5 has been prepared from OS3(CO)12 and P(OMe)3 by a combination of thermal and UV irradiation synthetic methods. An investigation by 31P and 13C NMR spectroscopy indicated that the mechanism of fluxionality in this compound probably involves the P(OMe)3 ligand of the Os(CO)3[P(OMe)3] unit moving from one equatorial site to the other via a trigonal twist mechanism. 相似文献
88.
This numerical simulation paper focuses on the adsorption/desorption of water in disordered mesoporous silica glasses (Vycor-like). The numerical adsorbent was previously obtained by off lattice method, and was shown to reproduce quite well the micro- and mesotextural properties of real Vycor, as well as morphological (pore size distribution) and topological (pore interconnections) disorder. The water-water interactions are described by the SPC model while water-silica interactions are calculated in the framework of the PN-TrAZ model. The water adsorption/desorption isotherms and the configurational energies are calculated by the Grand Canonical Monte Carlo simulation method. The low pressure results compare well with experiments, showing the good transferability of the intermolecular potential. It is shown that if the hysteresis loop observed in the adsorption/desorption isotherm is considered as a true phase transition (which is actually still an open question in the case of disordered porous materials), then it is possible to calculate the grand potential by applying the thermodynamic integration scheme. The grand potential is shown to be multivalued for low (subcritical) temperature, and continuous for high (supercritical) temperature. A coexistence point is found within the hysteresis loop, actually close to the vertical desorption line. Below the equilibrium chemical potential, the gaslike branch is stable whereas the liquidlike branch is metastable. The situation is reversed above the coexistence point. 相似文献
89.
The kinetics of the process AuCl3(nu) + Cl−→ AuCl
4
−
+ nu (nu = one of a number of five-membered N-donor heterocycles covering a wide range of basicity, namely: oxazole, 2,4,5-trimethyloxazole,
thiazole, 5-methylthiazole, 4-methylthiazole, 4,5-dimethylthiazole, 2,4-dimethylthiazole, 2,4,5-trimethylthiazole, imidazole
and 2-methylimidazole) have been studied in methanol at 25 °C. The reactions follow the usual two-term rate law, rate = (k
1 + k
2[Cl−])[complex], observed in a square-planar substitution associative-mechanism. The second-order rate constants, k
2, indicate that the discriminating ability of Au(III) in these complexes is good and markedly influenced by the nature of the leaving group. A linear-free-energy relationship,
logk
2 = 0.53pK
a
+ constant, is observed between the rate constant and the basicity of the leaving group for its replacement by chloride.
The results are compared with data from the literature regarding a series of complexes of the type AuCl3(py) (py = one of a number of pyridines) reacting with the Cl− anion under the same experimental conditions. The reactivity depends not only upon ligand basicity but also upon the nature
of the ligand in the order: pyridines> five-membered heterocycles. Steric factor due to the presence of a single methyl group
ortho to the sp2 nitrogen atom in the ring has no influence on the rate of substitution while, surprisingly, when there are two ortho methyl groups a remarkable steric retardation effect is observable. The results are discussed in terms of reaction-profile
in the associative-substitution reaction and bonding interactions in the ground and transition states. 相似文献
90.
Peter Wipf Roland Prevo Jost H. Bieri Gabriel Germain Heinz Heimgartner 《Helvetica chimica acta》1988,71(5):1177-1190
Thermal Generation and Reactions of (Benzylthio)-and (Arylthio)-Substituted Nitrile Ylides Thermolysis of 4-(benzylthio)- and 4-(arylthio)-1,3-oxazol-5(2H)-ones 6 , at 110–155° in the presence of dipolarophiles with activated C≡C, C?C, C?O, C?S, and N?N bonds, led to 5-membered cyclo-adducts and CO2 (cf. Schemes 3, 5-7). Heating 6a and 6c in the presence of ethyl propiolate yielded ethyl quinoline-3-carboxylate ( 19 ) and ethyl pyridine-3-carboxylate( 22 ), respectively (cf. Scheme 8). These results are rationalized on the basis of the intermediate formation of thio-substituted nitrile ylides of type 7 (cf. Scheme 2), which undergo regioselective 1,3-dipolar cycloadditions with reactive dipolarophiles. In the absence of such a dipolarophile, the nitrile ylides isomerize via a [1,4]-H shift to give 2-aza-1,3-butadienes of type 20 . The latter are trapped in a Diels-Alder reaction with ethyl propiolate (cf. Scheme 8). 相似文献