Density functional theory-based prediction of some aqueous-phase chemistry of superheavy element 111. Roentgenium(I) is the "softest" metal ion

A previous approach (Hancock, R. D.; Bartolotti, L. J. Inorg. Chem. 2005, 44, 7175) using DFT calculations to predict log K1 (formation constant) values for complexes of NH3 in aqueous solution was used to examine the solution chemistry of Rg(I) (element 111), which is a congener of Cu(I), Ag(I), and Au(I) in Group 1B. Rg(I) has as its most stable presently known isotope a t(1/2) of 3.6 s, so that its solution chemistry is not easily accessible. LFER (Linear free energy relationships) were established between DeltaE(g) calculated by DFT for the formation of monoamine complexes from the aquo ions in the gas phase, and DeltaG(aq) for the formation of the corresponding complexes in aqueous solution. For M2+, M3+, and M4+ ions, the gas-phase reaction was [M(H2O)6]n+(g) + NH3(g) = [M(H2O)5NH3]n+(g) + H2O(g) (1), while for M+ ions, the reaction was [M(H2O)2]+(g) + NH3(g) = [M(H2O)NH3]+(g) + H2O(g) (2). A value for DeltaG(aq) and for DeltaE for the formation of M = Cu2+ in reaction 1, not obtained previously, was calculated by DFT and shown to correlate well with the LFER obtained previously for other M2+ ions, supporting the LFER approach used here. The simpler use of DeltaE values instead of DeltaG(aq) values calculated by DFT for formation of monoamine complexes in the gas phase leads to LFER as good as the DeltaG-based correlations. Values of DeltaE were calculated by DFT to construct LFER with M+ = H+, and the Group 1B metal ions Cu+, Ag+, Au+, and Rg+, and with L = NH3, H2S, and PH3 in reaction 3: [M(H2O)2]+(g) + L(g) = [M(H2O)L]+g) + H2O(g) (3). Correlations involving DeltaE calculated by DMol3 for H+, Cu+, Ag+, and Au+ could reliably be used to construct LFER and estimate unknown log K1 values for Rg(I) complexes of NH3, PH3, and H2S calculated using the ADF (Amsterdam Density Functional) code. Log K1 values for Rg(I) complexes are predicted that suggest the Rg(I) ion to be a very strong Lewis acid that is extremely "soft" in the Pearson hard and soft acids and bases sense.     

Planar trimethylenemethane dianion chemistry of lanthanide metallocenes: synthesis, structure, density functional theory analysis, and reactivity of [(C5Me5)2Ln]2[mu-eta3:eta3-C(CH2)(3] Complexes

The unusual formation of planar trimethylenemethane (TMM) dianion complexes of lanthanide metallocenes, [(C5Me5)2Ln]2[mu-eta3:eta3-C(CH2)3] (Ln = Sm, 1; La, 2; Pr, 3; Nd, 4; Y, 5) has been examined by synthesizing examples with metals from La to Y to examine the effects of radial size on structure and to provide closed shell examples for direct comparison with density functional theory (DFT) calculations. Synthetic routes to 1-4 have been expanded from the [(C5Me5)2Ln][(mu-Ph)2BPh2]/neopentyl lithium reaction involving beta-methyl elimination to a [(C5Me5)2Ln][(mu-Ph)2BPh2]/isobutyl lithium route. The synthetic pathways are sensitive to metal radius. To obtain 5, the methylallyl complex, (C5Me5)2Y[CH2C(Me)CH2], 6, was synthesized and treated with [(C5Me5)2YH]x. In the Lu case, the neopentyl complex [(C5Me5)2LuCH2C(CH3)3]x, 7, was isolated instead of the TMM product. X-ray crystallography showed that the metrical parameters of the planar TMM dianions in each complex are similar. The structural data have been compared with DFT calculations on the closed-shell lanthanum and lutetium complexes that suggest only limited covalent interactions with the lanthanide ion. Benzophenone (2 equiv) reacts with 1 to expand the original four-carbon TMM skeleton to a dianionic bis(alkoxide) ligand containing a symmetrically substituted C=CH2 moiety in [(C5Me5)2Sm]2[mu-(OCPh2CH2)2C=CH2], 8. In this reaction, the TMM complex reacts as a bifunctional bisallylic reagent that generates an organic framework containing a central vinyl group.     

Metal-metal bonding in molecular actinide compounds: electronic structure of [M2X8](2-) (M = U, Np, Pu; X = Cl, Br, I) complexes and comparison with d-block analogues

Density functional and multiconfigurational (ab initio) calculations have been performed on [M(2)X(8)](2-) (X = Cl, Br, I) complexes of 4d (Mo, Tc, Ru), 5d (W, Re, Os), and 5f (U, Np, Pu) metals in order to investigate general trends, similarities and differences in the electronic structure and metal-metal bonding between f-block and d-block elements. Multiple metal-metal bonds consisting of a combination of sigma and pi interactions have been found in all species investigated, with delta-like interactions also occurring in the complexes of Tc, Re, Np, Ru, Os, and Pu. The molecular orbital analysis indicates that these metal-metal interactions possess predominantly d(z2) (sigma), d(xz) and d(yz) (pi), or d(xy) and d(x2-y2) (delta) character in the d-block species, and f(z3) (sigma), f(z2x) and f(z2y) (pi), or f(xyz) and f(z) (delta) character in the actinide systems. In the latter, all three (sigma, pi, delta) types of interaction exhibit bonding character, irrespective of whether the molecular symmetry is D(4h) or D(4d). By contrast, although the nature and properties of the sigma and pi bonds are largely similar for the D(4h) and D(4d) forms of the d-block complexes, the two most relevant metal-metal delta-like orbitals occur as a bonding and antibonding combination in D(4h) symmetry but as a nonbonding level in D(4d) symmetry. Multiconfigurational calculations have been performed on a subset of the actinide complexes, and show that a single electronic configuration plays a dominant role and corresponds to the lowest-energy configuration obtained using density functional theory.     

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PIFA-mediated synthesis of novel pyrazoloquinolin-4-ones as potential ligands for the estrogen receptor

A facile and efficient preparation of pyrazoloquinolin-4-ones, as potential ligands for the estrogen receptor, via a PIFA [phenyliodine(III)bis(trifluoroacetate)] promoted cyclization reaction with overall yields up to 29% over six steps is described. The employed strategy, based on an electrophilic amidation reaction as the key step of the synthesis, allows the generation of a diverse array of derivatives.     

On Dedekind’s problem for complete simple games

We state an integer linear programming formulation for the unique characterization of complete simple games, i.e. a special subclass of monotone Boolean functions. In order to apply the parametric Barvinok algorithm to obtain enumeration formulas for these discrete objects we provide a tailored decomposition of the integer programming formulation into a finite list of suitably chosen sub-cases. As for the original enumeration problem of Dedekind on Boolean functions we have to introduce some parameters to be able to derive exact formulas for small parameters. Recently, Freixas et al. have proven an enumeration formula for complete simple games with two types of voters. We will provide a shorter proof and a new enumeration formula for complete simple games with two minimal winning vectors.     

Modelling of a pyroshock test device

Pyroshocks are transient motions of structural elements due to explosive loading induced by the detonation of ordnance devices incorporated into or attached to the structure. In space programs the simulation of pyroshocks is a fixed part of the test requirement for instruments and equipments of space vehicles. Therefore, by the use of various test devices such as hammer pendulums the excitation of a pyroshock has to be reproduced which, so far, has led to rather empirical knowledge. In the current work a better predictability of pyroshocks is focussed in order to reduce the duration of test periods. As an approach numerical and analytical calculations are used for the simulation of in-plane wave propagation in rods and rectangular disks due to mechanical impacts. Furthermore, the results obtained from different mathematical and mechanical theories are compared with data received from conducted experiments. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A delayed class of BOLD waveforms associated with spreading depression in the feline cerebral cortex can be detected and characterised using independent component analysis (ICA)

An application of independent component analysis to blood oxygenation level- dependent MRI (BOLD-MRI) results was used to detect cerebrovascular changes that followed the initiation of cortical spreading depression (CSD) in feline brain. The cortical images were obtained from a horizontal plane at 28 s intervals before, and for 1.4-1.75 h after, KCl dissolved in agar (KCl/agar) had been directly applied to the left suprasylvian gyrus of 13 anesthetized cats for 10 min. It successfully resolved, for the first time, a novel class of prolonged, and delayed, biphasic BOLD waveforms. These were larger in amplitude ( approximately 20%), longer lasting and more delayed in onset (13-33 min) than the brief propagating (90 s) BOLD increase ( approximately 4%) already known to be associated with CSD on earlier occasions. Furthermore, such changes occurred in localized regions on the hemisphere ipsilateral to the site of stimulus application in 4 out of 5 control subjects rather than themselves generating propagating waves. Finally, the biphasic waveforms were consistently abolished in the 4 experimental animals studied following the i.v. administration of sumatriptan (0.3 mg kg(-1)), an antimigraine 5-HT(1B/1D) agonist, 15 min before the application of the transient stimulus. They were abolished in 2 out of 4 animals following the intraperitoneal (i.p.) administration of SB-220453 (tonabersat: 10 mg kg(-1), 90 min before stimulus application), a novel anticonvulsant that has recently been reported to inhibit CSD. ICA has thus been successful in detecting a novel localized, as opposed to propagating, signal of potential physiological significance hidden in complex BOLD- MRI data, whose sensitivity to sumatriptan may relate it to the cerebrovascular changes reported in the headache phase of migraine.     

Crossover scaling of wavelength selection in directional solidification of binary alloys

We simulate cellular and dendritic growth in directional solidification in dilute binary alloys using a phase-field model solved with adaptive-mesh refinement. The spacing of primary branches is examined for a wide range of thermal gradients and alloy compositions and is found to undergo a maximum as a function of pulling velocity, in agreement with experimental observations. We demonstrate that wavelength selection is unambiguously described by a nontrivial crossover scaling function from the emergence of cellular growth to the onset of dendritic fingers. This result is further validated using published experimental data, which obeys the same scaling function.