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991.
Nunes JP Figueira MJ Belo D Santos IC Ribeiro B Lopes EB Henriques RT Vidal-Gancedo J Veciana J Rovira C Almeida M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9841-9849
The gold and nickel bisdithiolene complexes based on new highly extended ligands incorporating fused tetrathiafulvalene and thiophene moieties (alpha-tdt=thiophenetetrathiafulvalenedithiolate and dtdt=dihydro- thiophenetetrathiafulvalenedithiolate), were prepared and characterised by using cyclic voltammetry, single crystal X-ray diffraction, EPR, magnetic susceptibility and electrical transport measurements. These complexes, initially obtained under anaerobic conditions as diamagnetic gold monoanic [nBu(4)N][Au(alpha-tdt)(2)] (4), [nBu(4)N][Au(dtdt)(2)] (3) and nickel dianionic species [(nBu(4)N)(2)][Ni(alpha-tdt)(2)] (8), [(nBu(4)N)(2)][Ni(dtdt)(2)] (7), can be easily oxidised to the stable neutral state just by air or iodine exposure. The monoanionic complexes crystallise in at least two polymorphs, all of which have good cation and anion segregation in alternated layers, the anion layers making a dense 2D network of short SS contacts. All of the neutral complexes, obtained as microcrystalline or quasi amorphous fine powder, present relatively large magnetic susceptibilities that correspond to effective magnetic moments in the range 1-3 mu(B) indicative of high spin states and very high electrical conductivity that in case of the Ni compound can reach sigma(RT) approximately 250 S cm(-1) with a clear metallic behaviour. These compounds are new examples of the still rare single-component molecular metals. 相似文献
992.
Santos LS Cunha RL Comasseto JV Eberlin MN 《Rapid communications in mass spectrometry : RCM》2007,21(9):1479-1484
Tellurium tetrachloride adds to alkynes via two pathways: a concerted syn-addition that yields Z-tri- and -tetrasubstituted alkenes or an anti-addition that yields E-alkenes. The mechanistic aspects of these divergent pathways for TeCl4 addition to alkynes have been investigated by on-line electrospray ionization (tandem) mass spectrometry (ESI-MS(/MS)). Via ESI-MS(/MS), we have been able to intercept and characterize the active electrophile TeCl3+ in tetrahydrofuran (THF) solutions of TeCl4, as well as its THF complex and several TeClx(OH)y+ derivatives. For the first time, also, key Te(IV) cationic intermediates of the electrophilic addition of TeCl4 to alkynes were captured for gas-phase MS investigation. The detailed structural data of cyclic tellurane intermediates intercepted herein seems to provide insights into the coordinative behavior of the Te(IV) atom and its mode of action towards biological targets. 相似文献
993.
Santos SF Santos ML Almeida LE Costa NB Gimenez IF Araki K Mayer I Engelmann FM Toma HE Barreto LS 《Journal of colloid and interface science》2007,305(2):264-269
In this work silica gels have been prepared by a sol-gel method using tetraethylorthosilicate as gel precursor. The tetraruthenated porphyrins H2(3-TRPyP), Co(3-TRPyP), and H2(4-TRPyP) were incorporated into the systems during gel formation without problems commonly found in the process, such as aggregation. Spectroscopic studies of the resulting silica gels revealed the presence of absorption bands in the range 200-400 nm associated with the transitions of the groups ruthenium-bipyridine, along with the Soret band at the same wavelengths observed in solution. The porphyrins were found to preserve fluorescence emission properties in the range 650-700 nm even after the aging period. Study of the thermal behavior and decomposition kinetics evidenced that the porphyrin H2(4-TRPyP) is the least stable of the group and that all compounds decompose according to first-order kinetics. 相似文献
994.
Fustero S Fernández B Sanz-Cervera JF Mateu N Mosulén S Carbajo RJ Pineda-Lucena A Ramírez de Arellano C 《The Journal of organic chemistry》2007,72(23):8716-8723
The synthesis of new chiral fluorinated amino and azamacrolactones of types 1 and 2 is described. A ring-closing metathesis (RCM) reaction constitutes the key step in this methodology, which uses fluorinated amino alcohols 7 as starting materials. The influence of the CF2 group, which is located in the alpha-position relative to the carbon bearing the amino group, on the efficiency of the RCM reaction is noteworthy. This method allows for the preparation of the desired fluorinated macrolactones in excellent yields. 相似文献
995.
de los Santos JM Ignacio R Aparicio D Palacios F 《The Journal of organic chemistry》2007,72(14):5202-5206
The synthesis of nitrosoalkenes derived from phosphine oxides and phosphonates generated through base-mediated dehydrohalogenations of readily available alpha-halooximes is reported. These highly reactive intermediates act as Michael acceptors toward nucleophilic reagents such as ammonia, amines, and optically active amino esters, furnishing alpha-amino phosphine oxides and phosphonates in a highly regioselective fashion. 相似文献
996.
Arroyo Y Rodríguez JF Santos M Tejedor MA Ruano JL 《The Journal of organic chemistry》2007,72(3):1035-1038
Reactions of (S)-alpha-(methylthio)-2-(p-tolylsulfinyl)benzyl carbanion with different carbonyl compounds proceeds with complete control of the configuration at the benzylic position. Aldehydes yield easily separable mixtures of beta-hydroxy sulfides, epimers at the hydroxylic carbon, where the stereoselectivity depends on steric factors (from 20% to >98% de). 相似文献
997.
Catarina Xavier Isabel Santos Roger Alberto 《Journal of organometallic chemistry》2007,692(6):1332-1339
A PNA monomer containing thymine as nucleobase (1) was synthesized, characterized and coupled to the pyrazolyl containing ligand 3,5-Me2pz(CH2)2N((CH2)3COOH)(CH2)2NHBoc (2) and to a modified cysteine S-(carboxymethyl-pentafluorphenyl)-N-[(trifluor)carbonyl]-l-cysteine methyl ester (3) yielding the bifunctional chelators 6 and 7, respectively. Reactions of 6 and 7 with the Re(I) tricarbonyl starting material [Re(CO)3(H2O)3]Br afforded the complexes fac-[Re(CO)3(κ3-6)]+ (8) and fac-[Re(CO)3(κ3-7)] (9), respectively. The identity of 8 and 9 has been established based on IR spectroscopy, elemental analysis, ESI-MS spectrometry and HPLC. The multinuclear NMR spectroscopy (1H, 13C, g-COSY, g-HSQC) has also been very informative in the case of complex 8, showing the presence of rotamers in solution. For 9 the NMR spectrum was too complex due to the presence of rotamers and diastereoisomers. The radioactive congeners of complexes 8 and 9, fac-[99mTc(CO)3(κ3-6)]+ (8a) and fac-[99mTc(CO)3(κ3-7)] (9a), have been prepared by reacting the precursor fac-[99mTc(CO)3(H2O)3]+ with the corresponding ligands being their identity established by comparing their HPLC chromatograms with the HPLC of the rhenium surrogates. 相似文献
998.
The solvent effect on rotation about the conjugated C-N bond has been studied for methyl N,N-dimethylcarbamate (1), S-methyl N,N-dimethylthiocarbamate (2), O-methyl N,N-dimethylthiocarbamate (3), and methyl N,N-dimethyldithiocarbamate (4). The present investigation included experimental determination of activation parameters (DeltaH, DeltaS, and DeltaG) combined with theoretical calculations via both quantum and classical approaches. Rotational barriers were measured through dynamic NMR experiments in solvents of varied polarity and proton donor ability. In the less polar solvents, the values were 15.3+/-0.5 (CS2), 14.0+/-1.1 (CS2), 17.5+/-0.4 (CCl4), and 14.6+/-0.5 kcal/mol (CCl4) for 1, 2, 3, and 4, respectively. Upon changing to an aqueous solution, the greatest variations occurred for 2 and 4, whereas for 1 and 3, there was no observable effect. Quantum chemical calculations at the HF/6-311+G(2d,p) and B3LYP/6-311+G(2d,p) levels, with the inclusion of solvation effects via the isodensity polarizable continuum model (IPCM), correctly reproduced the experimentally observed trends but failed to account for some of the measured rotational barrier's magnitudes. Hydrogen-bonding effects were included by performing molecular dynamic simulations. For these latter calculations, it was necessary to parametrize the force field against energies of water-solute complexes calculated at B3LYP/6-31+G(d,p). Through the results of radial distribution functions, solution rotational barriers could be calculated, presenting good agreement with experimental determinations and revealing the role of hydrogen bonding. Interestingly, only for 2, the rotational barrier is predicted to increase as a result of complexation with water. For the remaining compounds, hydrogen bonding causes the barrier to decrease, contrasting with most of the molecular systems studied up to now. 相似文献
999.
Eslava S Baklanov MR Kirschhock CE Iacopi F Aldea S Maex K Martens JA 《Langmuir : the ACS journal of surfaces and colloids》2007,23(26):12811-12816
Ellipsometric porosimetry was used to determine the adsorption isotherms of toluene, methanol, and water on b-oriented Silicalite-1 coatings with a thickness of less than ca. 250 nm and to obtain adsorption kinetics. The adsorption isotherms are of sufficient quality to reveal several aspects of the pore structure such as the adsorbate capacity and the adsorbate/framework affinity. The use of a combination of different molecular probes in ellipsometric porosimetry to elucidate the molecular accessibility of Silicalite-1 pores is demonstrated. It is shown that ellipsometric porosimetry is an appropriate technique for probing the influence of aging of the Silicalite-1 coating and of planarization polishing on the porosity, pore accessibility, and adsorbate/framework affinity. 相似文献
1000.
Initiated chemical vapor deposition (iCVD) of alternating copolymer thin films has been achieved for the first time. Copolymerization is desirable for maleic anhydride (Ma) since this monomer does not homopolymerize to an appreciable extent. At conditions where the observed deposition rates for styrene (S) and Ma homopolymers were only 0 and 5.5 nm/min, respectively, combining the two monomers resulted in a much higher deposition rate of 75.4 nm/min. iCVD processes utilize low energy (<30 W) to generate peroxy radicals from initiator molecules while avoiding degradation of functional groups in the monomers. Indeed, full retention of the anhydride functionality from the Ma monomer and avoidance of undesirable side reactions was observed in iCVD of poly(styrene-alt-maleic anhydride) (PSMa) copolymer films. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and 13C nuclear magnetic resonance (NMR) conclusively demonstrate that all of the copolymer films contain 50% styrene and 50% Ma (within experimental error), irrespective of gas feed ratios employed during the deposition. The 13C NMR signal in the 136-140 ppm region from the quaternary carbon in styrene and additional distortionless enhancement polarization transfer experiments confirmed that the copolymers are strictly alternating. Varying the gas feed ratio of Ma to styrene provided control over deposition rates and number-average molecular weights. Number-average molecular weights varied from 1380 to 4680 g/mol, and deposition rates varied from 6.3 to 75.4 nm/min. 相似文献