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901.
The use of reduced overlap population (ROP) analysis from EHMO calculations as a means to gauge the presence of metal–metal
bonds in triosmium clusters is examined. A number of triosmium clusters containing bridging ligands have been used as test
cases, including the bis-ethoxy bridged cluster Os3(μ-OEt)2(CO)10, 1b, and some of its group 15 derivatives Os3(μ-OEt)2(CO)9(EPh3), 2. These latter clusters are newly synthesized and have been characterized completely, including by single-crystal X-ray crystallographic
studies.
In honour of Professor Dieter Fenske on his 65th birthday. 相似文献
902.
The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature
of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom
in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net
resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two
junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface.
Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between
the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are
in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation
as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study
of the electrostatic potential at the position of the hydrogen nuclei.
We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive
life. 相似文献
903.
Characterization and determination of a complex mixture of fatty acid methyl esters was performed for commercial fish oil using two-dimensional GC-MS data coupled with resolution techniques. Various principle component analysis methods such as significant factor analysis and fixed size moving window evolving factor analysis were used for the number of factors, zero concentration and selective regions. Then, the convoluted chromatograms were resolved into pure chromatograms and mass spectra using heuristic evolving latent projections (HELP) method. Fatty acids of C16:1omega7, C18:4omega3, C18:1omega11, C18:1omega9, C18:0, C20:2omega6, C20:1omega9, C22:1omega11, C22:1omega9 and C24:1omega9 were resolved an fied by using similarity searches between deconvoluted mass spectra and MS database, in different parts of total ion current chromatogram. Window target testing factor analysis is also applied for confirming the presence or absence of target analytes. The results of the present work show that combination of hyphenated chromatographic methods and resolution techniques provide a complementary method for accurate analysis of real multi-component systems such as fish oil. 相似文献
904.
A multi-wall carbon nanotube (MWNT)/cetyl pyridine bromine (CPB) composite film modified glassy carbon electrode (GCE) was
developed for the electrochemical determination of hymecromone in phosphonate buffer. Electrochemical behaviour of hymecromone
at the composite film electrode was investigated with voltammetry. Compared with an irreversible oxidation of hymecromone
at the bare GCE, the oxidation peak current was enhanced greatly at the film electrode. Some parameters such as pH, scan rate,
accumulation potential and accumulation time were optimized. Under optimal conditions, an oxidation peak at 0.82 V was employed
to determine hymecromone electrochemically. A linearity between the oxidation peak current and the hymecromone concentration
was obtained in the range of 3.0 × 10−7 − 2.0 × 10−5 mol 1−1 with a detection limit of 8.0 × 10−8 mol 1−1. The proposed procedure was successfully applied to assay hymecromone in pharmaceutical formulation with satisfactory results.
The text was submitted by the authors in English. 相似文献
905.
Zhang De-Qing Wang Shao-Jun Sun Hong-Shan Wang Xiu-Li Cao Mao-Sheng 《Journal of Sol-Gel Science and Technology》2007,41(2):157-161
Lead zirconate titanate nanopowders Pb(Zr0.52Ti0.48)O3 (PZT) were prepared by modified sol-gel process in ethylene glycol system with zirconium nitrate as the zirconium source.
The research showed that it was critical to add lead acetate after the reaction of zirconium nitrate and tetrabutyl titanate
in ethylene glycol system for preparing PZT of exact titanium content. The reaction mechanisms of the sol synthesis, preparation
of xerogel and agglutinating process were characterized through using FT-IR, NMR, TG-FTIR, and GC-MS. The experiment proved
that ethylene glycol system did not rely on hydrolysis and condensation reactions in the process of the sol formation, but
on the formation of chain or network large molecules from complexation of ethylene glycol and all Ti and minor Pd, Zr. In
the preparation of xerogel, the complexation reaction was so completed that it formed large molecules network composed of
metal and dioxyethyl. Bulk weight loss happened before 350°C in the process of sintering xerogel to prepare PZT nanopowders.
Volatile matters and vapor phase decomposition resultants were primarily oxy-compounds including ethylene glycol, aldehyde-ketone
compounds, carbon dioxide and nitrate radical conversion matters. After 350°C, primary vapor phase decomposition resultants
were carbon dioxide and minor carbonyl compound. 相似文献
906.
Jian-yun Du 《Transition Metal Chemistry》2004,29(7):699-702
Two novel complexes, [Zn(dmatrz)2]Cl2
(1) and [Zn(dmatrz)2(SCN)2] (2), have been prepared and characterized by X-ray crystallography, absorption and luminescence spectrometries (dmatrz=3,5-dimethy-4-amino-1,2,4-triazole). The coordination environment of the zinc(II) ions in (1) and (2) has a distorted tetrahedral geometry completed via two independent nitrogen atoms of two triazole ligands and two anions, respectively. Both (1) and (2) show strong blue luminescence properties. Furthermore, (1) displays stronger blue photoluminescence than (2) as the result of different anions (Cl- and SCN-) coordinated to the zinc(II) ions. 相似文献
907.
Young-a Lee Sang Myung jung Shin Won kang Ok-sang Jung 《Transition Metal Chemistry》2004,29(7):710-713
A facile procedure for synthesizing the mono(hydroxo)tris(carboxylato)platinum(IV) species has been achieved. The reaction of [PtII(OH)2(dmpda)] (dmpda=2,2-dimethyl-1,3-propanediamine) with a 30% aqueous solution of H2O2 in the presence of a carboxylic acid produces a stable [PtIV(OOCR)3(OH)(dmpda)] (R=Me, Et) complex in high yield. The crystal structures of [PtIV(OOCMe)3(OH)(dmpda)] . H2O (triclinic P1 bar, a=8.761(2) Å, b=9.245(3) Å, c=10.659(2) Å, =106.25(2)°, =93.90(2)°, =98.92(2)°, V=813.1(3) Å3, Z=2, R= 0.0474) and [PtIV(OOCEt)3(OH)(dmpda)] (monoclinic P21/c, a=12.777(4) Å, b=10.514(2) Å, c=14.971(3) Å, =107.40(2)°, V=1919.2(8) Å3, Z=4, R=0.0611) show that the hydroxyl group has been selectively positioned at an axial site. The intramolecular hydrogen bond between the OH and C=O moiety exists (O(H)...=C, 2.83 Å for [PtIV(OOCMe)3(OH)(dmpda)] · H2O; 2.72 Å for [PtIV(OOCEt)3(OH)(dmpda)]. Formation of the axial-mono(hydroxo)tris(carboxylato)platinum(IV) species may be ascribed to a combination of `reactive-equatorial effects' with `cis-addition' in the carboxylic acid. 相似文献
908.
Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed. 相似文献
909.
Keith E. Johnson Richard M. Pagni John Bartmess 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1077-1101
Summary. A background for studying acids in various solvents is developed, emphasizing the importance of knowing to what extent a solvent
conducts electricity and is therefore ionized, the dissociation equilibria of common molecular solvents and the acidic and
basic species generated by solvent leveling. Acidity measurements in the atypical solvent water are discussed and the common
method of expressing acidity in other systems – by Hammett values – is introduced. Representative examples of reactions involving Br?nsted acids in ionic liquids are presented and attention paid to the questions of speciation and acidity values. It is found that
the gas phase proton affinity of a base is often a better guide to the acidity of its conjugate acid in an ionic liquid than
is the dissociation constant of the said acid in water. 相似文献
910.
The synthesis and anion binding properties of new ruthenium(II) and cobalt(II) phenanthroline complexes, containing two amide
subunits are described. Evidence for anion binding in dimethyl sulfoxide (DMSO) solution was obtained from u.v.–vis titration
experiments. Results indicated that these receptors showed strong affinity for F− and AcO−, and showed weak affinity for OH− and H2PO
4
−
, and showed no affinity for Cl−, Br−, I−. These receptors interacted with various anions examined through hydrogen-bond formation. 相似文献