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41.
Mary McPartlin 《Polyhedron》1984,3(12):1321-1328
The recently developed electron-counting rules for condensed polyhedral metal carbonyl clusters have been utilised to develop a systematic approach for enumerating the structural alternatives for metal cluster compounds which are isoelectronic. The more usual cluster degradation and aggregation processes are represented in a matrix form which relates the change in electron count to the number of new bonds formed (or broken). The matrices for cluster degradation and aggregation are represented in a complementary fashion so that the search for isoelectronic clusters greatly simplified. The utility of the approach is illustrated by reference to some recent examples from metal carbonyl cluster chemistry. 相似文献
42.
Ivo Ngeli Corine Baud GErald Bernardinelli Yvan Jacquier Mary Moraon Paul Müllet 《Helvetica chimica acta》1997,80(4):1087-1105
The [Rh2(OAc)4]-catalyzed decomposition of {[(4-nitrophenyl)sulfonyl]imino}phenyl-λ3-iodane (NsN?IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents. Scope and limitations of the reaction were investigated. Yields of up to 84% were achieved in the most favorable cases. Yields were enhanced by electron-releasing substituents and decreased by steric hindrance. Aziridination competed with allylic insertion with olefinic substrates. The insertion reaction proceeded with retention of configuration. With chiral RhII catalysts, a modest asymmetric induction was observed. A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed. 相似文献
43.
García F Hopkins AD Kowenicki RA McPartlin M Tesa Y 《Dalton transactions (Cambridge, England : 2003)》2004,(14):2051-2052
The reaction of (Me(3)Si)(3)SiK[middle dot]18-crown-6 with SbCl(3)(3 : 1 equiv.) provides a simple route to the title complex [(Me(3)Si)(3)SiSb](4). The potassium base initially acts as a nucleophile and then as a coupling agent, forming Sb-Sb bonds. 相似文献
44.
Born—Oppenheimer potential surfaces for a bridged three-site electron-transfer system are calculated. The adiabatic potentials depend upon both the vibrational sum and difference coordinates. Along the vibrational difference coordinate, the ground-state surface has single-minimun form when the through-bridge electronic coupling is strong, and double-minimum form for weak through-bridge coupling. The results are compared to those previously reported for two-site models. 相似文献
45.
2-Diethylaminoethanethiol hydrochloride is proposed for spectrophotometric determination of palladium(II). The sensitivity of the reaction is 0.0085 smg/cm2 and the yellow colored complex shows absorption maxima at 258 mμ and 303 mμ. Color development is slow in the cold but complete after heating for 10–15 min. The optimum pH range is 3.5 to 5.5 and the system adheres to Beer's law between 0.2 and 16.8 p.p.m. of palladium. The average and maximum relative standard deviations were 0.60% and 1.40% respectively. Interferences due to other platinum metals were studied and a procedure is suggested for the simultaneous determination of rhodium and palladium. 相似文献
46.
Hixson KK Rodriguez N Camp DG Strittmatter EF Lipton MS Smith RD 《Electrophoresis》2002,23(18):3224-3232
A method for the complete peptide mapping of the model integral membrane protein bacteri-orhodopsin is demonstrated. Utilizing more effective enzymatic digestion, procedures with capillary liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) and tandem mass spectrometry (MS/MS), all predicted tryptic digestion products were detected, as well as peptides from all previously reported post-translational modifications of bacteriorhodopsin. A significant contribution of chymotryptic-like digestion products was also observed. A characterization of the behavior of hydrophobic integral membrane peptides in a reversed-phase liquid chromatographic separation is also provided. The method reported here offers improved compatibility of the solubilizing reagents with both the chromatography and mass spectrometry, rendering it suitable for high-throughput proteomic applications. 相似文献
47.
Streeter I Wain AJ Thompson M Compton RG 《The journal of physical chemistry. B》2005,109(25):12636-12649
An in situ electrochemical electron spin resonance (ESR) study on the electro-oxidation of para-chloroaniline, para-bromoaniline, and para-iodoaniline dissolved in acetonitrile at gold electrodes is reported. ESR spectra obtained using a tubular flow cell reveal the presence of a paramagnetic dimer product derived from para-aminodiphenylamine, during oxidative electrolysis, suggesting the coupling of reactive electrogenerated radical cations with neutral parent haloaniline molecules. The ESR signal intensity behaves in a manner expected for a radical species reacting with second-order kinetics, suggesting the paramagnetic dimer is, itself, unstable. The theory describing the ESR signal intensity flow rate behavior for this reaction mechanism is developed for the tubular arrangement and used to extract mechanistic and kinetic data from the experimental results for the cases of para-chloroaniline and para-bromoaniline. Further mechanistic aspects, including proton and halide ion expulsion during dimerization, are explored voltammetrically and with the aid of digital simulations using Digisim. Comparison of the ESR signal and voltammetric measurements suggests that an additional mechanism operates which does not lead to paramagnetic products. Additionally, the in situ electrolysis of N,N-dimethyl-para-bromoaniline is reported to generate the stable radical cation of N,N,N',N'-tetramethylbenzidine, and a mechanism of electro-oxidation is, thus, proposed. 相似文献
48.
Bond AD García F Jantos K Lawson GT McPartlin M Wright DS 《Chemical communications (Cambridge, England)》2002,(12):1276-1277
The novel, deca-lithium cage [(mtaNHLi)(As2(Nmta)5)-Li(4).2thf]2 (1) (mtaN = 5-methylthiazolyl, C4H4N2S) contains an imido-bridged tetraanion [(mtaN)2As(mu-Nmta)-As(Nmta)2]4-, which represents a new type of multi-functional imido group 15 ligand framework (homologous with group 15 anions of the type [As(NR)3]3-). 相似文献
49.
The calculation of non-paired spatial orbitals and alternant molecular orbital wavefunctions for the benzyl radical is described. The NPSO and AMO methods give comparable energy lowerings which indicate that they make substantial allowance for electron correlation. The calculated spin densities are not in very good accord with experiment and it is thought that this reflects inadequacies in the integral approximations used. 相似文献
50.
Jane?Jin John?C.?Achenbach Shiping?ZhuEmail author Yingfu?Li 《Colloid and polymer science》2005,283(11):1197-1205
The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block
on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined
and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization
methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter
ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal
complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very
stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore
less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ
(DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers
showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG,
but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON. 相似文献