Spectroscopic and DFT investigation of [M{HB(3,5-iPr2pz)3}(SC6F5)] (M = Mn, Fe, Co, Ni, Cu, and Zn) model complexes: periodic trends in metal-thiolate bonding

A series of metal-varied [ML(SC6F5)] model complexes (where L = hydrotris(3,5-diisopropyl-1-pyrazolyl)borate and M = Mn, Fe, Co, Ni, Cu, and Zn) related to blue copper proteins has been studied by a combination of absorption, MCD, resonance Raman, and S K-edge X-ray absorption spectroscopies. Density functional calculations have been used to characterize these complexes and calculate their spectra. The observed variations in geometry, spectra, and bond energies are interpreted in terms of changes in the nature of metal-ligand bonding interactions. The metal 3d-ligand orbital interaction, which contributes to covalent bonding in these complexes, becomes stronger going from Mn(II) to Co(II) (the sigma contribution) and to Cu(II) (the pi contribution). This change in the covalency results from the increased effective nuclear charge of the metal atom in going from Mn(II) to Zn(II) and the change in the 3d orbital populations (d5-->d10). Ionic bonding also plays an important role in determining the overall strength of the ML(+)-SC6F5(-) interaction. However, there is a compensating effect: as the covalent contribution to the metal-ligand bonding increases, the ionic contribution decreases. These results provide insight into the Irving-Williams series, where it is found that the bonding of the ligand being replaced by the thiolate makes a major contribution to the observed order of the stability constants over the series of metal ions.     

Effects of substituents on the stability of phosphoranyl radicals

The effect of substituents on the geometries, apicophilicities, radical stabilization energies, and bond dissociation energies of (*)P(CH(3))(3)X (X = CH(3), SCH(3), OCH(3), OH, CN, CF(3), Ph) were studied via high-level ab initio molecular orbital calculations. Two alternative definitions for the radical stabilization energy (RSE) were considered: the standard RSE, in which radical stability is measured relative to H-P(CH(3))(3)X, and a new definition, the alpha-RSE, which measures stability relative to P(CH(3))(2)X. We show that these alternative definitions yield almost diametrically opposed trends; we argue that alpha-RSE provides a reasonable qualitative measure of relative radical stability, while the standard RSE qualitatively reflects the relative strength of the P-H bonds in the corresponding H-P(CH(3))(3)X phosphines. The (*)P(CH(3))(3)X radicals assume a trigonal-bipyramidal structure, with the X-group occupying an axial position, and the unpaired electron distributed between a 3p(sigma)-type orbital (that occupies the position of the "fifth ligand"), and the sigma orbitals of the axial bonds. Consistent with this picture, the radical is stabilized by resonance (along the axial bonds) with configurations such as X(-) P(*+)(CH(3))(3) and X(*) P(CH(3))(3). As a result, substituents that are strong sigma-acceptors (such as F, OH, or OCH(3)) or have weak P-X bonds (such as SCH(3)) stabilize these configurations, resulting in the largest apicophilicities and alpha-RSEs. Unsaturated pi-acceptor substituents (such as phenyl or CN) are weakly stabilizing and interact with the 3p(sigma)-type orbital via a through-space effect. As part of this work, we challenge the notion that phosphorus-centered radicals are more stable than carbon-centered radicals.     

Application of the νD/νH ratio to the assignment of C-H(D) and ring vibrations in the infrared spectra of imidazole and its deuterated analogues

The IR spectra (4000-150 cm^?1)of imidazole and its I-, 2,4,5- and 1,2,4,5-deuterated analogues are discussed. All twenty-one fundamental IR active imidazole vibrations are assigned by employing the ν^D/ν^H ratio which is defined as the ratio between the frequencies of corresponding IR bands in the spectra of a ring-deuterated heterocyclic (or aromatic) molecule and its normal analogue. The results suggest that some previously reported assignments require revision.     

3-Hydroxypyrrolidines from epoxysulfonamides and dimethylsulfoxonium methylide

N-Tosyl-protected 3-hydroxypyrrolidines are prepared by reaction of dimethylsulfoxonium methylide with readily available epoxysulfonamides.     

The long term impact of a coherence based model for mathematics intervention

This article presents a large-scale longitudinal study of hundreds of students across the state of Kentucky that participated in a dual-focus mathematics intervention initiative when they were in the third grade. Rather than an exclusive focus on intervention, this initiative focused on both (i) high quality pull-out intervention and (ii) coherence between pull-out intervention and classroom instruction. The study found that over half of the third grade intervention students that participated in this initiative were classified as “novice” (the lowest possible performance category) on state standardized mathematics assessments at the end of the third grade. However, over the course of the following four years, the novice reduction rate of these students was significantly (p < .01) greater than other novices in Kentucky that did not participate in the initiative. These findings indicate that when implementing intervention initiatives to help students that are struggling with mathematics, it may be important to establish coherence between pull-out intervention and classroom instruction. The long term impact of this approach among traditionally underrepresented minorities suggest that this publication may provide insight into important equity issues where long-term analyses may sometimes be needed to capture the full impact of intervention initiatives.     

An effective compactness theorem for Coxeter groups

Through highly non-constructive methods, works by Bestvina, Culler, Feighn, Morgan, Rips, Shalen, and Thurston show that if a finitely presented group does not split over a virtually solvable subgroup, then the space of its discrete and faithful actions on \mathbbHⁿ{\mathbb{H}^n} , modulo conjugation, is compact for all dimensions. Although this implies that the space of hyperbolic structures of such groups has finite diameter, the known methods do not give an explicit bound. We establish such a bound for Coxeter groups. We find that either the group splits over a virtually solvable subgroup or there is a constant C and a point in \mathbbHⁿ{\mathbb{H}^n} that is moved no more than C by any generator. The constant C depends only on the number of generators of the group, and is independent of the relators.     

The austenite microstructure evolution in a duplex stainless steel subjected to hot deformation

Abstract

The austenite microstructure evolution and softening processes have been studied in a 23Cr–6Ni–3Mo duplex stainless steel, comprising equal fractions of austenite and ferrite, deformed in uniaxial compression at 1000 °C using strain rates of 0.1 and 10 s^?1. The texture and microstructure evolution within austenite was similar in character for both the strain rate used. The observed large-scale subdivision of austenite grains/islands into complex-shaped deformation bands, typically separated by relatively wide transition regions, has been attributed to the complex strain fields within this phase. Organised, self-screening microband arrays were locally present within austenite and displayed a crystallographic character for a wide range of austenite orientations. The microband boundaries were aligned with the traces of {1?1?1} slip planes containing slip systems having high, although not necessarily the highest possible, Schmid factors. The slightly lower mean intercept length and higher mean misorientation obtained for the sub-boundaries at the higher strain rate can be ascribed to the expected more restricted dynamic recovery processes compared to the low strain rate case. Dynamic recrystallisation within austenite was extremely limited and mainly occurred via the strain-induced migration of the distorted original twin boundaries, followed by the formation of multiple twinning chains.     

Robust spatially resolved pressure measurements using MRI with novel buoyant advection-free preparations of stable microbubbles in polysaccharide gels

MRI of fluids containing lipid coated microbubbles has been shown to be an effective tool for measuring the local fluid pressure. However, the intrinsically buoyant nature of these microbubbles precludes lengthy measurements due to their vertical migration under gravity and pressure-induced coalescence. A novel preparation is presented which is shown to minimize both these effects for at least 25 min. By using a 2% polysaccharide gel base with a small concentration of glycerol and 1,2-distearoyl-sn-glycero-3-phosphocholine coated gas microbubbles, MR measurements are made for pressures between 0.95 and 1.44 bar. The signal drifts due to migration and amalgamation are shown to be minimized for such an experiment whilst yielding very high NMR sensitivities up to 38% signal change per bar.