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51.
Günter Haufe Manfred Mühlstädt Dr. Jürgen Graefe 《Monatshefte für Chemie / Chemical Monthly》1977,108(4):803-811
In addition totrans-2-bromocyclooctanol andtrans-1,2-dibromocyclooctane,cis-4-bromocyclooctanol,cis-1,4-dibromocyclooctane,trans-1,4-dibromocyclooctane, and (Z)-5-bromocyclooctene are obtained, when (Z)-cyclooctene is treated with N-bromosuccinimide in the presence of water. Similarly the methoxybromination of (Z)-cyclooctene gives transanular products. 相似文献
52.
Determination of Molecular Weights by Gel Chromatography of Oligoimidoamides of Phosphoric Acid. Oligoimidoamides of phosphoric acid were eluted with nonionic water on a Sephadex LH-20 column. The measured distribution coefficient of the oligoimidoamides of phosphoric acid was independent of sample concentration and pH of the eluent. Andrews equation was obeyed: a linear relation exist between elution volume and logarithm of molecular weight both cyclic and acyclic oligoimidoamides of phosphoric acid. 相似文献
53.
Breher F Rüegger H Mlakar M Rudolph M Deblon S Schönberg H Boulmaâz S Thomaier J Grützmacher H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):641-653
The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners. 相似文献
54.
In the past few years millimeter and submillimeter wave spectroscopy has been the backbone for modern molecular line astronomy. The detection of unstable and high-temperature molecular species in the interstellar environment has stimulated the development of methods of detecting molecular ions, radicals and unstable molecules in the laboratory by means of millimeter wave technology. Some of the recent experimental advances as well as the developments which have occurred in the analysis of high resolution rotational and vibrational spectra with regard to understanding molecular dynamics will be discussed. 相似文献
55.
Werner Schulze und Manfred Scheffler 《Fresenius' Journal of Analytical Chemistry》1967,226(5):395-401
Zusammenfassung Um Material zur Deutung des Mechanismus der Sorption von Sr2+-Ionen an Eisen(III)-hydroxid zu gewinnen, werden Meßreihen mitgeteilt, in denen die pH-Abhängigkeit der Sorption sowie deren Beeinflussung bei Fällung mit verschiedenen Basen (NaOH, Ammoniak, Trimethylamin, Benzylamin) untersucht wird. Aus den charakteristischen Unterschieden der Sorptionskurven muß gefolgert werden, daß die Art der Base für die Sorption eine wichtige Rolle spielt.
Summary The sorption of Sr2+ ions on iron(III) hydroxide was studied as a function of the pH, of the precipitating reagent (NaOH, ammonium hydroxide, benzylamine, trimethylamine), of the temperature and of the total concentration.The curves of the relative sorption vs. pH are found to show characteristic differences which have to be explained in a detailed theory of the mechanism.相似文献
56.
Pennington DA Coles SJ Hursthouse MB Bochmann M Lancaster SJ 《Chemical communications (Cambridge, England)》2005,(25):3150-3152
The mono(salicylaldiminato) complexes Ti{3-tBu-2-(O)C6H3CH=N(R)}Cl3(THF)(where R = C6H5, C6F5) react with the metallated pyrrolylaldiminato ligand, K[2-(C6H5NCH)C4H3N], to afford the first examples of hybrid salicylaldiminato-ligated octahedral titanium complexes; the pre-catalysts give from very high to extremely high ethene polymerisation productivities when activated with MAO. 相似文献
57.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献
58.
The reaction of (E,E,Z)-cyclododeca-1.5,9-triene (1) with NBS and methanol gives bicyclic tetrahydrofuran derivatives (3) and (4) as well as usual 1,2-addition products while the related reaction with (Z,E,Z)-cyclotrideca-1,5,9-triene (7) leads to the bicyclic tetrahydropyran derivative (6), in both cases like O-heterocyclization products as the result of transannular participation of a methoxy group. 相似文献
59.
Wolfgang A. Herrmann Cornelia Weber Manfred L. Ziegler Orhan Serhadli 《Journal of organometallic chemistry》1985,297(2):245-254
The diazoolefines of composition N2CCR2 (R/R = CH3/CH3 and(-CH2-)5) are suitable precursors of the corresponding vinylidene ligands CCR2. Thus, treatment of the RhRh complex [(η5-C5Me5)Rh(μ-CO)]2 (1) with the N-nitrosourethanes 2a and 2b, resp., in the presence of lithium t-butoxide yields the otherwise inaccessible μ-vinylidene complexes (μ-CCR2)[(η5-C5Me5)Rh(CO)]2 (R = CH3 (3a), R,R = (-CH2-)5 (3b)). The analogous cobalt compound (μ-CCMe2)[(η5-C5Me5)Co(CO)]2 (5a) is obtained similarly. This procedure extends the well-documented diazoalkane method for the synthesis of μ-alkylidene complexes to the less stable diazoalkenes. A single-crystal X-ray diffraction study of the dimethylvinylidene derivative 3a shows the CMe2 ligand to adopt an almost symmetrically metal-bridging position (d(RhC) 197.8(1) and 204.3(1) pm), with a rhodium-rhodium single bond completing a three-membered Rh2C-metallacycle (d(RhRh) 268.4(0) pm) analogous with cyclopropane. 相似文献
60.