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71.
72.
Dietmar Seyferth 《Journal of organometallic chemistry》1974,80(1):C18-C20
The preparation of dihapto {8-methylene)-1-naphthyl}bis(triphenyl-phosphine)platinum(II), involving an internal metallation reaction, is described. 相似文献
73.
The Unimolecular mass spectrometric fragmentations of the molecular ions of 1,3-diphenylpropane, 1-(7-cycloheptatrienyl)-2-phenylethane and the 1-phenyl-2-tolylethanes and their [d5]phenyl analogues have been investigated by metastable ion techniques and measurements of ionization and appearance energies. By comparing the formation of [C7H7]+, [C7H8]+?, [C8H8]+? and [C8H9]+ it is shown that the molecular ions of the four diaryl isomers do not undergo ring expansion reactions of the aromatic nuclei prior to these fragmentations. Conversely, the molecular ions of the cycloheptatrienyl isomer suffer in part a contraction of the 7-membered ring. From these results and from the measured ionization and appearance energies lower limits to the activation energies of these skeletal isomerizations have been estimated yielding E > 33±5 kcal mol?1 formonoalkylbenzene, E > 20 2±5 kc mol?1 for 7-alkylcycloheptatriene and E > 40±5 kcal mol?1 for dialkylvbenzene positive radical ions. Upper limits can be deduced from literature evidence yielding E < 45 kcal mol?1 for monoalkylbenzene and E < 53 kcal 4mol?1 for dialkylbenzene positive radical ions. The activation energy thus estimated for monoalkylbenzene is in excellent agreement with the recently calculated value(s) for the toluene ion. 相似文献
74.
By UV-excited photoelectron emission microscopy (UV-PEEM) we investigated the microscopic growth behavior of organic thin films using 3,4,9,10-perylene-tetracarboxylicacid dianhydride (PTCDA) on a Ag(1 1 1) single crystal substrate as example. Direct, real time observation allows to correlate the initial growth modes and the related kinetic parameters with substrate properties like terrace width, step density, and step bunches from the submonolayer range up to 5 layers or more. Above room temperature PTCDA grows in a Stranski–Krastanov fashion: after completion of the first two stable layers three-dimensional islands are formed. The nucleation density strongly depends on the temperature and the substrate morphology thus affecting the properties of the organic film. 相似文献
75.
Fink H Panne U Theisen M Niessner R Probst T Lin X 《Fresenius' Journal of Analytical Chemistry》2000,368(2-3):235-239
A new method for analysis of metal additives in recycled thermoplasts from electronic waste was developed, based on dissolving the samples in an organic solvent and subsequent analysis of the corresponding solutions or suspensions by total-reflection X-ray fluorescence spectroscopy (TXRF). The procedure proved to be considerably less time consuming than the conventional digestion of the polymer matrix. Additives containing Ti, Zn, Br, Cd, Sn, Sb, and Pb were analyzed in a hundred randomly selected samples from recycling, which provided an overview of the range of elemental concentrations in thermoplasts utilized for consumer electronics. The results were validated independently by instrumental neutron activation analysis (INAA), subsequent regression analysis confirmed the trueness of the chosen approach. 相似文献
76.
The Diels—Alder reactions of α-pyrone with Me3SiCCSiMe3, Me3SiCCSiMe2H, Me2HSiCCSiMe2H, Me3GeCCGeMe3, Me3SiCCGeMe3, Me3SiCCSnMe3 and EtCCEt were examined. All except the first two acetylenes gave the expected 1,2-disubstituted benzene product, in line with results obtained previously with Me3SnCCSnMe3. The first two acetylenes, Me3SiCCSiMe3 and Me3SiCCSiMe2H, also yielded benzene products containing substantial amounts of the 1,3-disubstituted benzenes, as well as minor amounts of the 1,4-isomers. This formation of unexpected isomers during these reactions was shown to result from acid-catalyzed rearrangement of the initially formed 1,2-disubstituted products, 1,2-(Me3Si)2C6H4 and 1-Me3Si-2-Me2HSiC6H4. The acidic impurities arose from pyrolysis of the bromobenzene solvent used or were introduced as contaminants of the α-pyrone. Such isomerizations were inhibited by addition of small amounts of triethylamine. The fact that no rearrangement took place with the other acetylenes is due to the scavenging of acidic impurities which might cause isomerization by the starting acetylene and the benzene product via metal—carbon bond cleavage processes. 相似文献
77.
The rhodium(I) complexes trans‐[Rh(diphos)(CO)Cl] 7 (diphos=pbpb), 8 (diphos=nbpb), and 9 (diphos=cbpb) were synthesized (Scheme 4) and used as catalysts for the carbonylation of MeOH to AcOH (Scheme 1). The trans coordination imposed by the rigid C‐spacer framework of the diphos ligands pbpb, nbpb, and cbpb, demonstrated by 31P‐NMR and IR spectroscopy of 7 – 9 and unambiguously confirmed by single‐crystal X‐ray structure analysis of 7 , improved the thermal stability of the rhodium(I) system under carbonylation conditions and, hence, the catalytic performance of the complexes. For the catalytic carbonylation of MeOH, the active catalyst could be prepared in situ from the mixture of [Rh(CO)2Cl]2 and the corresponding diphos ligand pbpb, nbpb, or cbpb, giving the same results as carbonylation in the presence of the isolated complexes 7, 8 or 9 (see Table). The highest activity was observed for complex 7 (or the mixture [Rh(CO)2Cl]2/pbpb, the catalytic turnover number (TON) being 950 after 15 min (170°, 22 bar). 相似文献
78.
Mercuration of η5-cyclopentadienyl-η4-tetraphenylcyclobutadienecobalt, followed by transmetalation with n-butyllithium and reaction of the lithium derivative with benzophenone gave η4-Ph4C4Coη5-C5H4CPh2OH. Treatment of this alcohol produced the [η4-Ph4C4CoC5H4CP2]+ cation. This species reacted as a carbon electrophile with methanol, monomethylamine and N-methylpyrrole, as a cobalt electrophile with N,N-dimethylaniline and anisole. In the latter process the C5H4CPh2 ligand was displaced and the η6-arene-η4-tetraphenylcyclobutadienecobalt complexes were formed. Similar reactions with benzene, toluene and mesitylene proceeded only in the presence of aluminum chloride. The bonding in the cation is discussed on the basis of this chemistry and 13C NMR studies. 相似文献
79.
The post-translational modifications of the 96 kDa protein dynamin A from Dictyostelium discoideum were analyzed using Q-TOF mass spectrometry. The accurate molecular mass of the intact protein revealed a covalent modification causing an additional mass of 42 Da. The modification could be identified as N-terminal acetylation by tandem mass spectrometry. Extracted ion chromatograms for the a(1) and b(1) ion of the tryptic T1 peptide were used to detect the acetylated peptide within 54 nanoelectrospray ionization tandem mass spectra. Owing to the accurate molecular mass of the intact protein, additional covalent modifications could be excluded. In addition to the covalent modification, the domain structure of dynamin A was determined by applying a combination of limited proteolysis, sodium dodecylsulfate polyacrylamide gel electrophoresis, automated tandem mass spectrometry and protein database searching. 相似文献
80.
Dietmar Rahner Stefan Machill Heike Schlörb Kerstin Siury Matthias Kloss Waldfried Plieth 《Journal of Solid State Electrochemistry》1998,2(2):78-84
An overview is given of intercalation materials for both the negative and the positive electrodes of lithium batteries, including
the results of our own research. As well as lithium metal as a negative electrode, we consider insertion materials based on
aluminium alloys. In the case of the positive electrode metal-oxides based on manganese, nickel and cobalt are discussed.
Received: 27 May 1997 / Accepted: 30 July 1997 相似文献