Women in modern economic society: demographic and geographic images and realities

With the approach of the Fourth World Conference on Women in Beijing, it is appropriate for scholars to reflect on the status of women in modern society, on the changes that ha ve occurred in that status, and on the plans for future changes

Sterically restricted tin phosphines, stabilized by weak intramolecular donor-acceptor interactions

Funding: Engineering and Physical Sciences Research Council (EPSRC)Four related sterically restricted pen-substituted acenaphthenes have been prepared containing mixed tin phosphorus moieties in the proximal 5,6-positions (Acenap[SnR3][(PPr2)-Pr-i]; Acenap = acenaphthene-5,6-diyl; R-3 = Ph-3 (1), Ph2Cl (2), Me2Cl (3), Bu2Cl (4)). The degree of intramolecular P-Sn bonding within the series was investigated by X-ray crystallography, solution and solid-state NMR spectroscopy, and density functional theory (DFT/B3LYP/SBKJC/PCM) calculations. All members of the series adopt a conformation such that the phosphorus lone pair is located directly opposite the tin center, promoting an intramolecular donor acceptor P -> Sn type interaction. The extent of covalent bonding between Sn and P is found to be much greater in triorganotin chlorides 2-4 in comparison with the triphenyl derivative 1. Coordination of a highly electronegative chlorine atom naturally increases the Lewis acidity of the tin center, enhancing the Ip(P)-sigma*(Sn-Y) donor acceptor 3c-4e type interaction, as indicated by conspicuously short Sn-P peri distances and significant (1)J(P-31,Sn-119) spin spin coupling constants (SSCCs) in the range 740-754 Hz. Evidence supporting the presence of this interaction was also found in solid-state NMR spectra of some of the compounds which exhibit an indirect spin spin coupling on the same order of magnitude as observed in solution. DFT calculations confirm the increased covalent bonding between P and Sn in 2-4, with notable WBIs of ca. 0.35 obtained, in comparison to 0.1 in 1.PostprintPeer reviewe

Nota del curatore

The authors thank EPSRC and NSERC (Canada) for financial support.Reactions of the dianion [Te(tBuN)P(μ-NtBu)2P(NtBu)Te]2− with I2 or [Cp*RhCl2]2 unexpectedly produced complexes of the novel spirocyclic Te5 dianion [{tBuN(Te)P(μ-NtBu)2P(Te)NtBu}2μ-Te]2−, which is N,N′-coordinated to two Na+ ions in the disodium derivative and adopts a Te,Te′,Te′′-bonding mode in the Cp*Rh complex.PostprintPeer reviewe

Toward Unbiased Galaxy Cluster Masses from Line of Sight Velocity Dispersions

We study the use of red sequence selected galaxy spectroscopy for unbiased estimation of galaxy cluster masses. We use the publicly available galaxy catalog produced using the semi-analytic model of De Lucia & Blaizot (2007) on the Millenium Simulation (Springel et al. 2005). We explore the impacts on selection using galaxy color, projected separation from the cluster center, and galaxy luminosity. We study the relationship between cluster mass and velocity dispersion and identify and characterize the following sources of bias and scatter: halo triaxiality, dynamical friction of red luminous galaxies and interlopers. We show that due to halo triaxiality the intrinsic scatter of estimated line of sight dynamical mass is about three times larger (30-40%) than the one estimated using the 3D velocity dispersion (~12%) and a small bias (~1%) is induced. We find evidence of increasing scatter as a function of redshift and provide a fitting formula to account for it. We characterize the amount of bias and scatter introduced by dynamical friction when using subsamples of red-luminous galaxies to estimate the velocity dispersion. We study the presence of interlopers in spectroscopic samples and their effect on the estimated cluster dynamical mass. Our results show that while cluster velocity dispersions extracted from a few dozen red sequence selected galaxies do not provide precise masses on a single cluster basis, an ensemble of cluster velocity dispersions can be combined to produce a precise calibration of a cluster survey mass observable relation. Currently, disagreements in the literature on simulated subhalo velocity dispersion mass relations place a systematic floor on velocity dispersion mass calibration at the 15% level in mass. We show that the selection related uncertainties are small by comparison, providing hope that with further improvements this systematic floor can be reduced.Comment: submitted to Ap

Synthesis and characterization of novel organic heteroatom compounds from reaction of Woollins’ Reagent with various organic substrates

A series of new selenium-containing heteroatom compounds were synthesized in good yields by the reactions of Woollins’ reagent with various organic substrates such as cyclohexanamine, N-benzoylbenzamide, benzoic anhydride, 4-fluoro-N-(2-oxo-2-phenylethyl)benzamide, N-benzoylbenzamide, benzoic anhydride, 3-(bromomethyl)benzonitrile, 1,2-diphenylethane-1,2-diol and sodium alcoholate. Three representative X-ray structures are described.PostprintPostprintPeer reviewe

Explicit Computation of Input Weights in Extreme Learning Machines

We present a closed form expression for initializing the input weights in a multi-layer perceptron, which can be used as the first step in synthesis of an Extreme Learning Ma-chine. The expression is based on the standard function for a separating hyperplane as computed in multilayer perceptrons and linear Support Vector Machines; that is, as a linear combination of input data samples. In the absence of supervised training for the input weights, random linear combinations of training data samples are used to project the input data to a higher dimensional hidden layer. The hidden layer weights are solved in the standard ELM fashion by computing the pseudoinverse of the hidden layer outputs and multiplying by the desired output values. All weights for this method can be computed in a single pass, and the resulting networks are more accurate and more consistent on some standard problems than regular ELM networks of the same size.Comment: In submission for the ELM 2014 Conferenc

Spirocyclic, macrocyclic and ladder complexes of coinage metals and mercury with dichalcogeno P2N2-supported anions

Financial support from the EPSRC and NSERC (Canada) is acknowledged.Metathetical reactions of alkali–metal derivatives of the dianion [tBuN(Se)P(μ-NtBu)2P(Se)NtBu]2− (2Se2−) with Ag(NHC)Cl, Ag[BF4], AuCl(THT) and HgCl2, as well as the reaction of 2S2− with AuCl(THT) were investigated. The observed products all incorporate the monoprotonated ligands 2SeH− or 2SH− in a variety of structural arrangements around the metal centres, including tetrameric and trimeric macrocycles [Ag and Au (E = Se)], a ladder (Au, E = S) and a spirocycle (Hg); the ladder contains both the dianion 2S2− and the monoanion 2SH− as ligands linking three Au2 units. All complexes have been characterised in the solid state by single crystal X-ray analyses and in solution by multinuclear (1H, 31P and 77Se) NMR spectra.PostprintPeer reviewe

Gravitational Flexion by Elliptical Dark Matter Haloes

We present equations for the gravitational lensing flexion expected for an elliptical lens mass distribution. These can be reduced to one-dimensional finite integrals, thus saving significant computing time over a full two-dimensional calculation. We estimate constraints on galaxy halo ellipticities for a range of potential future surveys, finding that the constraints from the two different types of flexion are comparable and are up to two orders of magnitude tighter than those from shear. Flexion therefore appears to be a very promising potential tool for constraining the shapes of galaxy haloes from future surveys.Comment: 7 pages, 5 figures, submitted to MNRA

Sterically encumbered tin and phosphorus peri-substituted acenaphthenes

The work in this project was supported by the Engineering and Physical Sciences Research Council (EPSRC), EaStCHEM and the University of St Andrews.A group of sterically encumbered peri-substituted acenaphthenes have been prepared, containing tin moieties at the 5,6-positions in 1 – 3 ([Acenap(SnR3)2], Acenap = acenaphthene-5,6-diyl; R3 = Ph3 ( 1 ), Me3 ( 2 ); [(Acenap)2(SnMe2)2] ( 3 )) and phosphorus functional groups at the proximal peri-positions in 4 and 5 ([Acenap(PR2)(PiPr2)] R2 = Ph2 ( 4 ), Ph(iPr) ( 5 )). Bis(stannane) structures 1 – 3 are dominated by repulsive interactions between the bulky tin groups, leading to peri-distances approaching the sum of van der Waals radii. Conversely, the quasi-linear CPh-P···P three-body fragments found in bis(phosphine) 4 suggest the presence of a lp(P)−σ*(P–C) donor–acceptor 3c-4e type interaction, supported by a notably short intramolecular P···P distance and notably large JPP through-space coupling (180 Hz). Severely strained bis(sulfides) 4-S and 5-S , experiencing pronounced in-plane and out-of-plane displacements of the exocyclic peri-bonds, have also been isolated following treatment of 4 and 5 with sulfur. The resulting nonbonded intramolecular P···P distances, ∼4.05 Å and ∼12% longer than twice the van der Waals radii of P (3.60 Å), are among the largest ever reported peri-separations, independent of the heteroatoms involved, and comparable to the distance found in 1 containing the larger Sn atoms (4.07 Å). In addition we report two metal complexes with square planar [( 4 )PtCl2] ( 4-Pt ) and octahedral cis-[( 4 )Mo(CO)4] ( 4-Mo ) geometries. In both complexes the bis(phosphine) backbone is distorted, but notably less so than in bis(sulfide) 4-S . All compounds were fully characterized, and except for bis(phosphine) 5 , crystal structures were determined.PostprintPostprintPeer reviewe