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91.
Moudam O Kaeser A Delavaux-Nicot B Duhayon C Holler M Accorsi G Armaroli N Séguy I Navarro J Destruel P Nierengarten JF 《Chemical communications (Cambridge, England)》2007,(29):3077-3079
Homo- and heteroleptic copper(I) complexes obtained from various chelating bis-phosphine ligands and Cu(CH3CN)4BF4 have been used for the preparation of light emitting devices. 相似文献
92.
Charge Effects in PCP Pincer Complexes of NiII bearing Phosphinite and Imidazol(i)ophosphine Coordinating Jaws: From Synthesis to Catalysis through Bonding Analysis 下载免费PDF全文
Dr. Boris Vabre Dr. Yves Canac Dr. Christine Lepetit Dr. Carine Duhayon Prof. Remi Chauvin Prof. Davit Zargarian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17403-17414
This contribution reports on a new family of NiII pincer complexes featuring phosphinite and functional imidazolyl arms. The proligands RPIMCHOPR′ react at room temperature with NiII precursors to give the corresponding complexes [(RPIMCOPR′)NiBr], where RPIMCOPR=κP,κC,κP‐{2‐(R′2PO),6‐(R2PC3H2N2)C6H3}, R=iPr, R′=iPr ( 3 b , 84 %) or Ph ( 3 c , 45 %). Selective N‐methylation of the imidazole imine moiety in 3 b by MeOTf (OTf=OSO2CF3) gave the corresponding imidazoliophosphine [(iPrPIMIOCOPiPr)NiBr][OTf], 4 b , in 89 % yield (iPrPIMIOCOPiPr=κP,κC,κP‐{2‐(iPr2PO),6‐(iPr2PC4H5N2)C6H3}). Treating 4 b with NaOEt led to the NHC derivative [(NHCCOPiPr)NiBr], 5 b , in 47 % yield (NHCCOPiPr=κP,κC,κC‐{2‐(iPr2PO),6‐(C4H5N2)C6H3)}). The bromo derivatives 3–5 were then treated with AgOTf in acetonitrile to give the corresponding cationic species [(RPIMCOPR)Ni(MeCN)][OTf] [R=Ph, 6 a (89 %) or iPr, 6 b (90 %)], [(RPIMIOCOPR)Ni(MeCN)][OTf]2 [R=Ph, 7 a (79 %) or iPr, 7 b (88 %)], and [(NHCCOPR)Ni(MeCN)][OTf] [R=Ph, 8 a (85 %) or iPr, 8 b (84 %)]. All new complexes have been characterized by NMR and IR spectroscopy, whereas 3 b , 3 c , 5 b , 6 b , and 8 a were also subjected to X‐ray diffraction studies. The acetonitrile adducts 6 – 8 were further studied by using various theoretical analysis tools. In the presence of excess nitrile and amine, the cationic acetonitrile adducts 6 – 8 catalyze hydroamination of nitriles to give unsymmetrical amidines with catalytic turnover numbers of up to 95. 相似文献
93.
Two‐Coordinate Iron(I) Complex [Fe{N(SiMe3)2}2]−: Synthesis,Properties, and Redox Activity 下载免费PDF全文
Dr. C. Gunnar Werncke Philip C. Bunting Dr. Carine Duhayon Prof. Jeffrey R. Long Dr. Sébastien Bontemps Dr. Sylviane Sabo‐Etienne 《Angewandte Chemie (International ed. in English)》2015,54(1):245-248
First‐row two‐coordinate complexes are attracting much interest. Herein, we report the high‐yield isolation of the linear two‐coordinate iron(I) complex salt [K(L)][Fe{N(SiMe3)2}2] (L=18‐crown‐6 or crypt‐222) through the reduction of either [Fe{N(SiMe3)2}2] or its three‐coordinate phosphine adduct [Fe{N(SiMe3)2}2(PCy3)]. Detailed characterization is gained through X‐ray diffraction, variable‐temperature NMR spectroscopy, and magnetic susceptibility studies. One‐ and two‐electron oxidation through reaction with I2 is further found to afford the corresponding iodo iron(II) and diiodo iron(III) complexes. 相似文献
94.
The objective of this work was to optimize the ultrasound (US) pretreatment of sludge. Three types of sewage sludge were examined: mixed, secondary and secondary after partial methanisation (“digested” sludge). Thereby, several main process parameters were varied separately or simultaneously: stirrer speed, total solid content of sludge (TS), thermal operating conditions (adiabatic vs. isothermal), ultrasonic power input (PUS), specific energy input (ES), and for the first time external pressure. This parametric study was mainly performed for the mixed sludge. Five different TS concentrations of sludge (12–36 g/L) were tested for different values of ES (7000–75,000 kJ/kgTS) and 28 g/L was found as the optimum value according to the solubilized chemical oxygen demand in the liquid phase (SCOD). PUS of 75–150 W was investigated under controlled temperature and the “high power input – short duration” procedure was the most effective at a given ES. The temperature increase in adiabatic US application significantly improved SCOD compared to isothermal conditions. With PUS of 150 W, the effect of external pressure was investigated in the range of 1–16 bar under isothermal and adiabatic conditions for two types of sludge: an optimum pressure of about 2 bar was found regardless of temperature conditions and ES values. Under isothermal conditions, the resulting improvement of sludge disintegration efficacy as compared to atmospheric pressure was by 22–67% and 26–37% for mixed and secondary sludge, respectively. Besides, mean particle diameter (D[4,3]) of the three sludge types decreased respectively from 408, 117, and 110 μm to about 94–97, 37–42, and 36–40 μm regardless of sonication conditions, and the size reduction process was much faster than COD extraction. 相似文献
95.
Pasatoiu TD Tiseanu C Madalan AM Jurca B Duhayon C Sutter JP Andruh M 《Inorganic chemistry》2011,50(13):5879-5889
Herein, we report the synthesis, structural investigation, and magnetic and photophysical properties of a series of 13 [Zn(II)Ln(III)] heterodinuclear complexes, which have been obtained employing a Schiff-base compartmental ligand derived from o-vanillin [H(2)valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)]. The complexes have been synthesized starting from the [Zn(valpn)(H(2)O)] mononuclear compound and the corresponding lanthanide nitrates. The crystallographic investigation indicated two structural types: the first one, [Zn(H(2)O)(valpn)Ln(III)(O(2)NO)(3)], contains 10-coordinated Ln(III) ions, while in the second one, [Zn(ONO(2))(valpn)Ln(III)(H(2)O)(O(2)NO)(2)]·2H(2)O, the rare earth ions are nine-coordinated. The Zn(II) ions always display a square-pyramidal geometry. The first structural type encompasses the larger Ln ions (4f(0)-4f(9)), while the second is found for the smaller ions (4f(8)-4f(11)). The dysprosium derivative crystallizes in both forms. Luminescence studies for the heterodinuclear compounds containing Nd(III), Sm(III), Tb(III), Dy(III), and Yb(III) revealed that the [Zn(valpn)(H(2)O)] moiety acts as an antenna. The magnetic properties for the paramagnetic [Zn(II)Ln(III)] complexes have been investigated. 相似文献
96.
Pasatoiu TD Sutter JP Madalan AM Fellah FZ Duhayon C Andruh M 《Inorganic chemistry》2011,50(13):5890-5898
A series of dinuclear [Ni(II)Ln(III)] Schiff-base complexes (using a Schiff-base dicompartmental ligand derived from o-vanillin [H(2)valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)]) with Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and a hydroxo-bridged tetranuclear [Ni(II)Yb(III)] are reported. The crystal structures have been solved for 10 dinuclear complexes revealing four arrangements for the dinuclear units, which are modulated by the coordinated solvent molecules and the nitrato-anion interactions. The magnetic behaviors have been investigated, and the nature of the Ni(II)-Ln(III) exchange interaction has been emphasized by comparison with the behavior of the related [Zn(II)Ln(III)] derivatives. This allowed for establishing that the interaction within these compounds is antiferromagnetic with the 4f ions of the beginning of the Ln series and turns ferromagnetic from Gd(III) toward the end of the series. AC susceptibility investigations clearly show the occurrence of slow relaxation processes of the magnetization close to 2 K for the dinuclear [Ni(II)Dy(III)] complex. 相似文献
97.
This paper evaluates simple schemes to extrapolate potential energy values using the set of energies and forces extracted from a molecular dynamics trajectory. In general, such a scheme affords the maximum amount of information about a molecular system at minimal computational cost. More specifically, schemes like this are very important in the field of adaptive multi-scale molecular dynamics simulations. In this field, often the computation of potential energy values at certain trajectory points is not required for the simulation itself, but solely for the a posteriori analysis of the simulation data. Extrapolating the values at these points from the available data can save considerable computational time. A set of extrapolation schemes are employed based on Taylor series and central finite difference approximations. The schemes are first tested on the trajectories of molecular systems of varying sizes, obtained at MM and QM level using velocity-Verlet integration with standard simulation time steps. Remarkably good accuracy was obtained with some of the approximations, while the failure of others can be explained in terms of the distinct features of a molecular dynamics trajectory. We have found that, for a Taylor expansion of the potential energy, both a first and a second order truncation exhibit errors that grow with system size. In contrast, the second order central finite difference approximation displays an accuracy that is independent of the size of the system, while giving a very good estimate of the energy, and costing as little as a first order truncation of the Taylor series. A fourth order central finite difference approximation requires more input data, which is not always available in adaptive multi-scale simulations. Furthermore, this approximation gives errors of similar magnitude or larger than its second order counterpart, at standard simulation time steps. This leads to the conclusion that a second order central finite difference approximation is the optimal choice for energy extrapolation from molecular dynamics trajectories. This finding is confirmed in a final application to the analysis of an adaptive multi-scale simulation. 相似文献
98.
The preparation of versatile azaspiro[3.3]heptanes carrying multiple exit vectors is disclosed. Expedient synthetic routes enable the straightforward access to these novel modules that are expected to have significance in drug discovery and design. 相似文献
99.
Ludovic Daumont Alain Jenouvrier Semen Mikhailenko Michel Carleer Christian Hermans Sophie Fally Ann Carine Vandaele 《Journal of Quantitative Spectroscopy & Radiative Transfer》2012,113(11):878-888
High-resolution water vapor absorption spectra have been measured at room temperature in the 8800–11,600 cm?1 spectral region. They were obtained using the mobile BRUKER IFS 120M Fourier transform spectrometer (FTS) from ULB-SCQP coupled to the 50 m base long multiple reflection White type cell in GSMA laboratory. The absorption path was 600 m and different H2O/HDO/D2O mixtures were used. Measurements of line positions, intensities and self-broadening coefficients were performed for the HD16O isotopologue. 6464 rovibrational assignment of the observed lines was made on the basis of global variational predictions and allowed the identification of new energy levels. 3ν3, 2ν1+ν3, 3ν1+ν2, ν1+2ν3 and 2ν2+2ν3 are the five strongest bands. The present paper provides a complementary data set on water vapor for atmospheric and astrophysical applications. 相似文献
100.
Carine Eng Jean-Mary Simone Akane Hartenbach François Loiseau Reinhard Neier 《Monatshefte für Chemie / Chemical Monthly》2009,41(3):349-354
Abstract The macrocyclisation of hydroxyethylfuranyl acetic acid and of dehydrogenated model compounds of nonactic acid was investigated
to develop a facile synthesis of nonactin analogues. By applying the Yamagushi macrocyclisation to our ω-hydroxyacids, we were able to isolate a mixture of di-, tri-, tetra- and pentameric macrocycles.
Graphical abstract
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