Congested ferrocenyl polyphosphanes bearing electron-donating or electron-withdrawing phosphanyl groups: assessment of metallocene conformation from NMR spin couplings and use in palladium-catalyzed chloroarenes activation

The synthesis of novel substituted cyclopentadienyl salts that incorporate both a congested branched alkyl group (tert-butyl, (triphenyl)methyl, or tri(4-tert-butyl)phenylmethyl) and a phosphanyl group is reported. The introduction of either electron-withdrawing or electron-donating substituents (furyl, i-propyl, cyclohexyl, tert-butyl) on P atoms was generally achieved in high yield. The modular synthesis of ferrocenyl polyphosphanes from an assembly of these cyclopentadienyl salts was investigated, leading to the formation of new triphosphanes (denoted as 9-12) and diphosphanes (denoted as 14-16). The resulting phosphanes are not sensitive to air or moisture, even when electron-rich substituents are present. This set of polyphosphanes displays varied conformational features, which are discussed in the light of their multinuclear NMR characterization in solution and of the X-ray solid state structure of the representative triphosphane 1,2-bis(diphenylphosphanyl)-1'-(diisopropylphosphanyl)-3'-(triphenyl)methyl-4-tert-butyl ferrocene, 11. In particular, the existence of a range of significantly different nonbonded ("through-space", TS) spin-spin coupling constants between heteroannular P atoms, for the triphosphanes of this class, allowed their preferred conformation in solution to be appraised. The study evidences an unanticipated flexibility of the ferrocene platform, despite the presence of very congested tert-butyl and trityl groups. Herein, we show that, contrary to our first belief, the preferred conformation for the backbone of ferrocenyl polyphosphanes can not only depend on the hindrance of the groups decorating the cyclopentadienyl rings but is also a function of the substituents of the phosphanyl groups. The interest of these robust phosphanes as ligands was illustrated in palladium catalysis for the arylation of n-butyl furan with chloroarenes, using direct C-H activation of the heteroaromatic in the presence of low metal/ligand loadings (0.5-1.0 mol?%). Thus, 4-chlorobenzonitrile, 4-chloronitrobenzene, 4-chloropropiophenone, and 4-(trifluoromethyl)chlorobenzene were efficiently coupled to n-butyl furan, using Pd(OAc)(2) associated to the new diphosphane ligands 1,1'-bis(diisopropylphosphanyl)-3,3'-di(triphenyl)methyl ferrocene (15) or 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenyl)methylferrocene (16), which respectively hold the electron-rich -Pi-Pr(2) and -PCy(2) groups.     

Localized 5f electrons in superconducting PuCoIn?: consequences for superconductivity in PuCoGa?

The physical properties of the first In analog of the PuMGa(5) (M = Co, Rh) family of superconductors, PuCoIn(5), are reported. With its unit cell volume being 28% larger than that of PuCoGa(5), the characteristic spin-fluctuation energy scale of PuCoIn(5) is three to four times smaller than that of PuCoGa(5), which suggests that the Pu 5f electrons are in a more localized state relative to PuCoGa(5). This raises the possibility that the high superconducting transition temperature T(c) = 18.5 K of PuCoGa(5) stems from the proximity to a valence instability, while the superconductivity at T(c) = 2.5 K of PuCoIn(5) is mediated by antiferromagnetic spin fluctuations associated with a quantum critical point.     

Real-time near-field acoustic holography for continuously visualizing nonstationary acoustic fields

Near-field acoustic holography (NAH) is an effective tool for visualizing acoustic sources from pressure measurements made in the near-field of sources using a microphone array. The method involving the Fourier transform and some processing in the frequency-wavenumber domain is suitable for the study of stationary acoustic sources, providing an image of the spatial acoustic field for one frequency. When the behavior of acoustic sources fluctuates in time, NAH may not be used. Unlike time domain holography or transient method, the method proposed in the paper needs no transformation in the frequency domain or any assumption about local stationary properties. It is based on a time formulation of forward sound prediction or backward sound radiation in the time-wavenumber domain. The propagation is described by an analytic impulse response used to define a digital filter. The implementation of one filter in forward propagation and its inverse to recover the acoustic field on the source plane implies by simulations that real-time NAH is viable. Since a numerical filter is used rather than a Fourier transform of the time-signal, the emission on a point of the source may be rebuilt continuously and used for other post-processing applications.     

Modeling laser-generated guided waves in bonded plates by the finite element method

The purpose of this research is to develop an effective model of the transient laser-generated guided waves in bonded plates by the finite element (FE) method. The FE parameters, such as the mesh density and the time step size, which are related to wave propagation, are optimized in order to set up a standard, and the correlation between these parameters is discussed. The waveforms in bonded plates with different bonded interface modeled by the spring model are obtained and then compared. The results show that the transient responses are sensitive to the stiffness coefficients characterizing the cohesive quality. Finally, these FE results are compared with analytical and experimental results. All these comparisons confirm the accuracy of the FE method for modeling laser-generated guided waves in bonded plates.     

Use of in situ Mössbauer spectroscopy for electrochemical reactions involving57Fe

An electrochemical cell and relevant electrodes have been carried out in order to study in situ various electrochemical reactions involving iron using⁵⁷Fe Mössbauer resonance. The electrochemical behaviour of iron in strongly alkaline solution (KOH 5N) in the potential range (?1200<E相似文献   

Spectroscopic characterization of metal chloride/polyamide complexes

Complexes formed between metal halides MX_n (M=Li, Zn, Fe; X=Cl, Br) and an amorphous polyamide have been characterized by Infrared and Raman spectroscopies. They provide examples of the large variety of situations which can be generated by varying the concentration of the salts and their Lewis acidity. The LiX salts are dissociated and the lithium ion interacts with four amide oxygens or less, depending on the concentration, while the anion establishes N-H...X⁻ hydrogen bonds. Complexes with LiTFSI exhibit some ionic conductivity. Zinc halides are complexed under the form of a bent ZnX₂ molecule strongly coordinated to two or one amide oxygens depending on the concentration. Finally, FeCl₃ is ionized in the whole investigated concentration range into FeCl ₄ ⁻ and FeCl₂(L) ₄ ⁺ where L is the amide ligand coordinated to iron by its oxygen. Paper presented at the 2nd Euroconference on Solid State Ionics in Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Improved proton affinity measurements for proline and modified prolines using triple quadrupole and ion trap mass spectrometers

Proton affinity (PA) of compounds such as proline, cis-3-methylproline, cis-3-ethylproline, cis-3-isopropylproline and cis-3-isopentanylproline was determined by kinetic method with amines as the reference bases. The effective temperatures determined using ion trap and triple quadrupole mass spectrometers were found to be significantly different. In the case of the triple quadrupole instruments, the effective temperature depends significantly on the collision energy. The influence of the apparent basicity (GBapp) on the effective temperature may be used to estimate the difference in protonation entropy (DeltaDeltaS degrees) between the sample and reference compounds. In case of the ion trap mass spectrometer, the variation of the effective temperature as a function of the excitation amplitude is small, so it is difficult to account for the contribution of the entropy effects to the proton affinity value. A better estimation of the PA and DeltaDeltaS degrees values for the investigated molecules is obtained by combining the GBapp and Teff data pairs that are obtained from both the mass spectrometers.     

Proton affinity of diastereoisomers of modified prolines using the kinetic method and density functional theory calculations: role of the cis/trans substituent on the endo/exo ring conformation

The proton affinity (PA) of cis/trans-3-prolinoleucines and cis/trans-3-prolinoglutamic acids have been studied by the kinetic method and density functional theory (DFT) calculations. Several conformations of the neutral and the protonated modified prolines, in particular the endo and exo ring conformations, were analyzed with respect to their contribution to the PA values. When the substituent is an alkyl, both the diastereoisomers have the same PA value. However, the PA values for the diastereoisomers are different when the substituted chain contains functional groups (e.g. a carboxyl group). This variation in PA values could be attributed to the existence of intramolecular hydrogen bonds.     

Molecular dynamics simulation studies of the conformation and lateral mobility of a charged adsorbate biomolecule: implications for estimating the critical value of the radius of a pore in porous media

The conformations, the values of the lateral transport coefficient of a charged biomolecule (desmopressin) in the adsorbed layer and in the liquid layers above the adsorbed layer, the potential energies of the interaction between the biomolecules located in different liquid layers with the charged solid surface and with the biomolecules in the adsorbed layer, the potential energies of the interaction between water molecules in the hydration layers surrounding the conformations of the biomolecules in different layers, as well as the structure and number of hydration layers between the different conformations of desmopressin, were determined by molecular dynamics simulation studies. The results show that the lateral mobility of the adsorbed desmopressin is approximately equal to zero and the value of the lateral transport coefficient of the biomolecule in the liquid layers located above the adsorbed layer increases as the distance of the liquid layer from the charged solid surface increases. But the values of the lateral transport coefficient of the biomolecule in the liquid layers above the adsorbed layer are lower in magnitude than the value of the transport coefficient of desmopressin along the direction normal to the charged solid surface in the liquid phase located above the vacant charged sites of the solid surface, and these differences in the values of the transport coefficients have important implications with respect to the replenishment of the biomolecules in the inner parts of a channel (pore), the overall rate of adsorption, and the form of the constitutive equations that would have to be used in macroscopic models to describe the mechanisms of mass transfer and adsorption in the pores of adsorbent media. Furthermore, a novel method is presented in this work that utilizes the information about the sizes of the conformations of the biomolecule in the adsorbed layer and in the liquid layers above the adsorbed layer along the direction that is normal to the charged solid surface, as well as the number and size of the hydration layers along the same direction, and could be used to estimate the value of the lower bound of the linear characteristic dimension of a pore (i.e., pore radius) in porous adsorbent media (e.g., porous adsorbent particles; skeletons of porous monoliths) in order to realize effective transport and overall adsorption rate.     

Alkynes as masked ylides: gold-catalysed intermolecular reactions of propargylic carboxylates with sulfides

The in situ-generation of sulfur ylides by the gold-catalysed rearrangement of propargylic carboxylates in the presence of sulfides has resulted in highly efficient and novel transformations.