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41.
The [Et4N][M(CO)5SCOPh] complexes (1a, M = Mo; 2a, M = W) have been prepared at ambient temperatures by reacting the photogenerated M(CO)5 THF intermediate with [Et4N][SCOPh] in THF. Kinetic studies of the reactions of the anions [M(CO)5SCOPh]– with the tri(iso-propyl)phosphite (L) ligand under pseudo-first-order conditions indicate that these reactions are first-order in substrate and are independent of the P(OPr-i)3 concentration. It is thus envisaged that these CO substitutions proceed via a mechanism which involves initial cis-M—CO bond-breaking, followed by fast attack of the incoming nucleophile on the resulting intermediate to give [cis-M(CO)4{P(O-Pri)3}SCOPh]–. This facile displacement of cis-CO indicates the labilizing nature of the thiobenzoate ligand, most probably by virtue of distal oxygen atom participation. Activation parameters for the reactions are: [M(CO)5SCOPh]– + L cis-[M(CO)4(L)SCOPh]– + CO M = Mo, H
= 24.6(2) kcal mol–1, S
= 8.2(6) eu; M = W, H
= 28.4(2) kcal mol–1, S
= 11.3(5) eu. Kinetic data and the mechanism of these ligand-substitutions are discussed. 相似文献
42.
Vibrational properties (band position, infrared [IR], and Raman intensities) of C?N stretching mode were studied in 65 gas phase hydrogen‐bonded 1:1 complexes of HCN with OH acids and NH acids using density functional theory (DFT) calculations at the B3LYP‐6‐311++G(d,p) level. Furthermore, general characteristics of the hydrogen bonds and vibrational changes in acids OH/NH stretching bands were also considered. Experimentally observed blue shift of the C?N stretching band promoted by hydrogen bonding, which shortens the triple bond length, is very well reproduced and quantitatively depends on the hydrogen bond length. Both IR and Raman ν(C?N) band intensities are enhanced, also in good agreement with the experimental results. IR intensity increase is a direct function of the hydrogen bond energy. However, the predicted Raman intensity raise is a more complex function, depending simultaneously on characteristics of both the hydrogen bond (C?N bond length) and the H‐donating acid (polarizability). With these two parameters, ν (C?N) Raman intensities of the complexes are explained with a mean error of ±2.4%. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
43.
Summary
We give an intrinsic (set theoretical) method to obtain all realcompletions of a Tychonoff space X. It is based on the concept of a spectral structure. Every realcompletion of the space can be obtained as a space of terminal clusters relative to an appropriate spectral structure on X. Various applications of this concept are then given. For example we may characterize those spectral structures which yield the realcompletions between X and X, or which yield spaces that are realcomplete (that is, realcompact), or compact or pseudocompact or Lindelöf. We also determine the class K of compactifications K of X for which X will be real closed in K for every K K.Here we continue the use of the word realcompletion (see [2]) in place of real-compactification. As many investigations have shown and as the present article reinforces, the former is more appropriate than the latter. 相似文献
44.
J.W. Guthrie M.S.A. Salam C.A. Murimboh C.L. Chakrabarti D.C. Grégoire 《Analytica chimica acta》2005,528(2):205-218
Complexation of Ni(II), Cu(II), Zn(II), and Cd(II) by dissolved organic carbon (DOC) in some freshwater lakes in Rouyn-Noranda, Québec, Canada, where they were impacted by effluents from a nearby copper smelter, was measured by kinetic and equilibrium methods using cathodic and anodic stripping voltammetry. The measured free-metal-ion and labile metal-complex concentrations were compared with the predictions made by a widely-used computer speciation model, the Windermere Humic Aqueous Model (WHAM): WHAM V and its improved version WHAM VI. If it is assumed that 65% of the DOC is “active”, i.e. behaving as isolated humic substances such as fulvic acid, both versions of WHAM are able to predict the labile and free-metal-ion concentrations of Ni, Zn, and Cd reasonably well; however, both underestimate the free-copper-ion concentration by one to two orders of magnitude. WHAM VI is generally better than or equal to WHAM V for successfully predicting most of the free-metal-ion concentrations. The modelled competition by Al(III) and Fe(III) in the lake surface waters showed that in most cases Cu(II) was most affected by this competition. WHAM VI predicts a larger effect from the Al(III) and Fe(III) competition than does WHAM V. 相似文献
45.
M.?Prasad S.?P.?MoulikEmail author A. Al.?Wardian S.?Moore A.?van?Bommel R.?PalepuEmail author 《Colloid and polymer science》2005,283(8):887-897
The clouding points (CP) of the nonionic surfactants p-tert-octyl phenyl polyoxyethylene ether (Triton X 100), Brij-56 and Brij-97, and the water soluble polymer polyvinylmethylether (PVME) have been measured in the presence of the ionic surfactants alkyl (C10, C12, C14 and C16) triphenyl phosphonium bromides (ATPBs). The threshold additive concentrations required for efficient CP enhancement of the systems that were studied have been determined. Considering CP as the threshold state of phase separation, the energetics of the process at different additive concentrations has been evaluated. The spontaneity of free energy of the clouding process (G
c
0
) at the transition concentrations followed the order PVME > TX 100 Bj 56 > Bj 97. The clouding process has been found to be energetically endothermic with fairly large enthalpy and entropy changes that nicely compensate each other. The compensation temperature has been evaluated and compared with different types of the clouding agents.This revised version was published online in January 2005 with corrections to the names of the authors. 相似文献
46.
5‐Acetyl‐3‐amino‐4‐aryl‐6‐methylthieno[2,3‐b]pyridine‐2‐carboxamides ( 5a,b ) were reacted with triethyl orthoformate or nitrous acid to give the corresponding pyrimidinones 6a,b and triazinones 7a,b . The reaction of 5a,b with acetic anhydride was carried out and its products were identified as a mixture of 8‐acetyl‐9‐aryl‐2,7‐dimethylpyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidine‐4(3H)‐one ( 9a,b ) and related 5‐acetyl‐4‐aryl‐3‐biacetylamino‐6‐methylthieno[2,3‐b]pyridine‐2‐carbonitrile ( 10a,b ). Reaction of 7a with some halocompounds afforded the N‐alkylated triazinones 8a‐c . Chlorination of 6a,b and 9a,b with phosphorus oxychloride produced 4‐chloropyrimidines 11a‐d which were used as precursors for the rest of the target heterocycles. Some of the prepared compounds were tested in vitro for their antimicrobial activities. 相似文献
47.
N. Sh. Lebedeva R. S. Kumeev G. A. Al’per E. V. Parfenyuk A. S. Vashurin T. V. Tararykina 《Journal of solution chemistry》2007,36(6):793-801
For the first time the interactions between zinc(II)tetra-4-alkoxybenzoyloxiphthalocyanine (Zn(4—O—CO—C6H4—OC11H23)Pc) and 1,4-diazabicyclo[2.2.2]octane (DABCO) in o-xylene and chloroform have been studied by calorimetric titration and NMR and electron absorption spectroscopic methods.
It has been found that in o-xylene at concentrations of Zn(4—O—CO—C6H4—OC11H23)Pc higher than 6×10−4 mol⋅L−1
π–π dimers species are formed (λ
max= 685 nm). Additions of DABCO to the solution up to mole ratio 1 : 8 (Zn(4—O—CO—C6H4—OC11H23)Pc : DABCO) lead to a shift of the aggregation equilibrium towards monomer species due to formation of monoligand axial complexes.
Further increasing the DABCO concentration results in formation of Zn(4—O—CO—C6H4—OC11H23)Pc—DABCO—Zn(4—O—CO—C6H4—OC11H23)Pc sandwich dimers (λ
max= 675 nm). 相似文献
48.
Abdullah A. Al‐Karim Al‐Shara'ey 《中国化学会会志》2004,51(3):547-552
6‐Aryl‐5‐cyano‐4‐pyrimidinone‐2‐thion derivatives 1a‐c reacted with methyl iodide (1:2) to give the corresponding 2‐S,N‐dimethyl pyrimidine‐4‐one derivatives 2a‐c . Compounds 2a‐c were in turn, reacted with hydrazine hydrate to give the sulfur free reaction products 3a‐c . These reaction products were taken as the starting materials for the synthesis of several new heterocyclic derivatives. Reaction of 3a‐c with acetic anhydride and formic acid gave pyrimido triazines 4a‐c and 7a‐c , respectively. Their reactions with active methylene containing reagents gave the corresponding 2‐(1‐pyrazonyl)‐N‐methyl pyrimidine derivatives 9a‐c and 10a‐c , respectively. Their reactions with aromatic aldehydes afforded the corresponding 2‐hydrazono pyrimidine derivatives 11a‐c . The structure of these reactions products were established based on both elemental analysis and spectral data studies. 相似文献
49.
Contreras Ricardo R. Fontal Bernardo Bahsas Alí Suárez Trino Reyes Marisela Bellandi Fernando Nava Flor Cancines Pedro 《Transition Metal Chemistry》2004,29(1):51-55
The synthesis of [benzyl-N,N-alkylbis(2-amino-1-cyclopentencarbodithioate)]MII [alkyl = ethene (L2) and propene, (L3) and M = Cu, Ni and Co] complexes and their characterization (u.v.–vis., FT-IR, 1H-n.m.r., mass spectra and cyclic voltametry) are reported. 相似文献
50.
E. D. Totchasov M. Yu. Nikiforov O. V. Eliseeva G. A. Al’per 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2006,80(10):1676-1679
This work presents the results obtained in measurements of the kinematic viscosity and density of the methanol-n-nonane, ethanol-n-nonane, and ethanol-n-decane systems at various temperatures and low n-alkane concentrations (within the concentration range of miscibility). The dynamic viscosities of these systems at 298.15 K were calculated according to free volume theory. The results substantiated the existence of an anomaly in the behavior of viscosity of the methanol-n-nonane system (positive Δlnη values) and its absence for the ethanol-n-alkane systems. 相似文献