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991.
al-Ktaifani MM Bauer W Bergsträsser U Breit B Francis MD Heinemann FW Hitchcock PB Mack A Nixon JF Pritzkow H Regitz M Zeller M Zenneck U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(11):2622-2633
Several independent synthetic routes are described leading to the formation of a novel unsaturated tetracyclic phosphorus carbon cage compound tBu4C4P6 (1), which undergoes a light-induced valence isomerization to produce the first hexaphosphapentaprismane cage tBu4C4P6 (2). A second unsaturated isomer tBu4C4P6 (9) of 1 and the bis-[W(CO)5] complex 13 of 1 are stable towards similar isomerization reactions. Another starting material for the synthesis of the hexaphosphapentaprismane cage tBu4C4P6 (2) is the trimeric mercury complex [(tBu4C4P6)Hg]3 (11), which undergoes elimination of mercury to afford the title compound 2. Single-crystal X-ray structural determinations have been carried out on compounds 1, 2, 9, 11, and 13. 相似文献
992.
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
993.
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
994.
Karen L. Frindell Matthew R. Robinson Alois Popitsch 《Journal of solid state chemistry》2003,172(1):81-88
Selected photoluminescence in the wavelength range of 600-1540 nm is generated by energy transfer from a light-gathering mesostructured host lattice to an appropriate rare earth ion. The mesoporous titania thin films, which have a well-ordered pore structure and two-phase walls made of amorphous titania and TiO2 nanocrystallites, were doped with up to 8 mol% lanthanide ions, and the ordered structure of the material was preserved. Exciting the titania in its band gap results in energy transfer and it is possible to observe photoluminescence from the crystal field states of the rare earth ions. This process is successful for certain rare earth ions (Sm3+, Eu3+, Yb3+, Nd3+, Er3+) and not for others (Tb3+, Tm3+). A mechanism has been proposed to explain this phenomenon, which involves energy transfer through surface states on titania nanocrystals to matching electronic states on the rare earth ions. 相似文献
995.
Smith AB Pitram SM Gaunt MJ Kozmin SA 《Journal of the American Chemical Society》2002,124(49):14516-14517
High chemoselectivity can be achieved in the addition of lithium dithiane anions to vinyl epoxides exploiting the steric nature of the dithiane substituent. Unencumbered dithiane anions afford SN2 adducts, whereas sterically encumbered anions lead primarily to SN2' adducts. Furthermore, the SN2' addition occurs syn to the vinyl epoxide. 相似文献
996.
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
997.
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
998.
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
999.
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
1000.
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