Iron-catalyzed reductive radical cyclization of organic halides in the presence of NaBH4: evidence of an active hydrido iron(I) catalyst

Iron made'em: iron(II) complexes such as FeCl(2) and [FeCl(2)(dppe)(2) ] (dppe=1,2-bisdiphenylphosphinoethane) are efficient precatalysts for the radical cyclization of unsaturated iodides and bromides in the presence of NaBH(4). Cyclic voltammetry studies suggests that the reaction occurs through a radical mechanism via an anionic hydrido iron(I) species as the key intermediate for the activation of the substrates by electron transfer.     

Transition state theory thermal rate constants and RRKM‐based branching ratios for the N(2D) + CH4 reaction based on multi‐sState and multi‐reference Ab Initio calculations of interest for the titan's chemistry

Multireference single and double configuration interaction (MRCI) calculations including Davidson (+Q) or Pople (+P) corrections have been conducted in this work for the reactants, products, and extrema of the doublet ground state potential energy surface involved in the N( ² D) + CH₄ reaction. Such highly correlated ab initio calculations are then compared with previous PMP4, CCSD(T), W1, and DFT/B3LYP studies. Large relative differences are observed in particular for the transition state in the entrance channel resolving the disagreement between previous ab initio calculations. We confirm the existence of a small but positive potential barrier (3.86 ± 0.84 kJ mol^?1 (MR‐AQCC) and 3.89 kJ mol^?1 (MRCI+P)) in the entrance channel of the title reaction. The correlation is seen to change significantly the energetic position of the two minima and five saddle points of this system together with the dissociation channels but not their relative order. The influence of the electronic correlation into the energetic of the system is clearly demonstrated by the thermal rate constant evaluation and it temperature dependance by means of the transition state theory. Indeed, only MRCI values are able to reproduce the experimental rate constant of the title reaction and its behavior with temperature. Similarly, product branching ratios, evaluated by means of unimolecular RRKM theory, confirm the NH production of Umemoto et al., whereas previous works based on less accurate ab initio calculations failed. We confirm the previous findings that the N( ² D) + CH₄ reaction proceeds via an insertion–dissociation mechanism and that the dominant product channels are CH₂NH + H and CH₃ + NH. © 2012 Wiley Periodicals, Inc.     

Longitudinal NLO properties of C2H2, HCCF,and C2F2: Electron correlation and vibration effects

Electron correlation and vibration effects on longitudinal nonlinear optical properties of acetylene (C₂H₂), fluoroacetylene (HCCF), and difluoroacetylene (C₂F₂) have been studied using various quantum chemistry methods, including the second‐order perturbation theory (MP2); coupled cluster approach with singles, doubles (CCSD), and noniterative triples (CCSD(T)); and density functional methods (B3LYP and B98). Evaluation of the static and dynamic vibration (nuclear relaxation) contributions was based on the finite field relaxation method. Particular attention has been devoted to the assessment of the electron correlation effects on the nuclear relaxation contributions to the molecular properties. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Radical Cyclization/β-Elimination Tandem Reactions: Enantiopure Sulfoxides as Temporary Chiral Auxiliaries

Alkylidene-substituted cyclopentane derivatives are formed in high enantiomeric purity by the reaction shown below. A highly diastereoselective radical cyclization is followed by elimination of a β-sulfinyl radical. Interestingly, the addition of the Lewis acid methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) totally reverses the stereochemical outcome of the reaction. E=CO₂Me.     

Film formation from monodisperse acrylic lattices 2. Influence of drying temperature on the film formation process

The influence of drying temperature on the properties of latex films was investigated by gravimetry, turbidimetry (i.e., analysis of transmission spectra and interference), atomic force microscopy and measurement of water vapor permeability. Several pitfalls in the determination of water content of dried films that absorb water after being submerged in it have been proposed, such as fading boundaries, remaining water after drying and change of particle sizes. At moderately higher temperatures film formation is improved. This improvement follows from the formation of smoother film surfaces (AFM), lower water vapor permeabilities and smaller values for delta lambda(min). On the other hand, defects as cracks and channels also are created, especially at high temperatures. It appears, however, that these channels do not run from the one surface of a film to the other.     

Tuning and stability of a continuous-wave mid-infrared high-power single resonant optical parametric oscillator

A 2.2-W continuous-wave, continuously tunable, single-frequency OPO has been developed in the 3.0–3.8 μm wavelength range for the detection of molecular trace gasses. The oscillation threshold, output power and stability of the single resonant OPO were improved by optimizing pump beam waist and OPO cavity length. Both air-spaced and solid etalons were tested to frequency stabilize and tune the OPO, from which the solid etalon gave a better performance. Temperature oscillations in the PPLN crystal caused oscillations in the idler wavelength of less than 200 MHz over 300 s; the short-term stability was less than 3 MHz over 1 s. The high laser power, in combination with photoacoustic spectroscopy, achieved a detection limit of 10 parts-per-trillion for ethane in nitrogen. Received: 9 April 2002 / Revised version: 14 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax:+31-24/3653311, E-Mail: maartenh@sci.kun.nl     

2H( 3He, t)2p reaction at 2 GeV

The exclusive ²H( ³He, t)2p reaction has been studied at 2 GeV for energy transfers up to 500 MeV and triton angles up to 3.4^°. The protons were measured in the large acceptance magnetic detector DIOGENE, in coincidence with the forward tritons detected in a dedicated magnetic arm. The energy transfer spectra extend well above the pion threshold. However, in the region of Δ excitation, the yield is less than 10% of the inclusive ²H( ³He, t) cross-section, which indicates the small contribution of the ΔN ↦ NN process. The angular distributions of the two protons in their center of mass have been analysed as a function of energy transfer and triton angle and a Legendre polynomial decomposition has been achieved. These data have been compared to a model based on a coupled-channel approach for describing the NN and NΔ systems. Received: 21 October 2002 / Accepted: 15 November 2002 / Published online: 11 March 2003 RID="a" ID="a"e-mail: ramstein@ipno.in2p3.fr RID="†" ID="†"Deceased. RID="†" ID="†"Deceased. RID="d" ID="d"Present adress: School of Engineering, J?nk?ping University, P.O. Box 1026, S-551 11 J?nk?ping, Sweden. Communicated by M. Gar?on     

Experimental study of AO and T1 modes of the concert harp

String instruments are usually composed of a set of strings, a soundboard, and a soundbox with sound holes, which is generally designed to increase the sound level by using the acoustic resonances of the cavity. In the case of the harp, the soundbox and especially the sound holes are primarily designed to allow access to the strings for their mounting. An experimental modal analysis, associated to measurements of the acoustic velocity in the holes, shows the importance of two particular modes labeled A0 and T1 as it was done for the guitar and the violin. Their mode shapes involve coupled motions of the soundboard's bending and of the oscillations of the air pistons located in the sound holes. The A0 mode is found above the frequency of the lowest acoustically significant structural mode T1. Thus, the instrument does not really take advantage of the soundbox resonance to increase its radiated sound in low frequencies. However, contribution of mode A0 is clearly visible in the response of the instrument, confirming the importance of the coupling between the soundboard and the cavity.     

Phase transitions in self-dual generalizations of the Baxter–Wu model

We study two types of generalized Baxter–Wu models, by means of transfer-matrix and Monte Carlo techniques. The first generalization allows for different couplings in the up- and down-triangles, and the second generalization is to a q-state spin model with three-spin interactions. Both generalizations lead to self-dual models, so that the probable locations of the phase transitions follow. Our numerical analysis confirms that phase transitions occur at the self-dual points. For both generalizations of the Baxter–Wu model, the phase transitions appear to be discontinuous.     

Application of polarized neutron reflectometry and X-ray resonant magnetic reflectometry for determining the inhomogeneous magnetic structure in Fe/Gd multilayers

The evolution of the magnetic structure of multilayer [Fe (35 Å)/Gd (50 Å)₅] with variation in temperature and an applied magnetic field was determined using a complementary approach combining polarized neutron and X-ray resonant magnetic reflectometry. Self-consistent simultaneous analysis of X-ray and neutron spectra allowed us to determine the elemental and depth profiles in the multilayer structure with unprecedented accuracy, including the identification of an inhomogeneous intralayer magnetic structure with near-atomic resolution.