Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF)(6)](2)[(Cp6Sm6Se13)-Sm-t] and [Li(LHF4](2)[Cp6Nd6Se13]

The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp ' Ln(THF)](2)(mu (2)-Cl)(2)(mu (3)-Cl)(3)Na(THF)}(n) [Cp ' = eta (5)-' BuC5H4; Ln = Nd (1a), Sm (1b), Gd (1c), Yb (1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl(3), with NaCp ' in THF solution. Complex 1b reacts with Na2Se5 to give hexanuclear samarium polyselenide complexes [Na(THF)(6)](2)[Cp-6' SM6(mu (6)-Se)(mu -Se-2)(6)] (2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF)(4)](2)[Cp6Nd6(mu (6)-Se)(mu -Se-2)(6)] (3) is synthesized by the reaction of [CpNdCl2. 2LiCl . 5THF] with Na2Se5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms. (C) 2001 Elsevier Science BN. All rights reserved.

Half-sandwich metal diselenolate complexes Cp#M(NO)(SePh)(2) (M = Mo or W; Cp# = Cp or MeCp) as ligands. Synthesis of selenolate-bridged heterobimetallic compounds

The reactions of half-sandwich diselenolate Mo and W complexes (CpM)-M-#(NO)(SePh)(2) (M = Mo; Cp-# = Cp' (1a), MeCp (1b); M = W; Cp-# = Cp' (1c)) with (Norb)Mo(CO)(4), Ni(COD)(2) and Fe(CO)(5) have been investigated. Treatment of (1a), (1b) and (1c) with (Norb)Mo(CO)(4) in PhMe gave the bimetallic complexes: Cp'Mo(NO)(mu -SePh)(2)Mo(CO)(4) (2a), MeCpMo(NO)(mu -SePh)(2)Mo(CO)(4) (2b) and Cp'W(NO)(mu -SePh)(2)Mo(CO)(4) (2c) in moderate yields. Irradiation of (1a) and (1c) in the presence of Fe(CO)(5) gave heterobimetallic complexes Cp'Mo(CO)(mu -SePh)(2)Fe(CO)(3) (3a) and Cp'W(NO)(mu -SePh)(2)Fe(CO)(3) (3c). Ni(COD)(2) reacts with two equivalents of (1a), (1b) and (1c) to give [Cp'Mo(NO)(mu -SePh)(2)](2)Ni (4a), [MeCpMo(NO)(mu -SePh)(2)](2)Ni (4b) and [Cp'W(NO)(mu -SePh)(2)](2)Ni (4c) in good yields. The new heterobimetallic complexes were characterized by i.r., H-1-n.m.r., C-13-n.m.r. and EI-MS spectroscopy.

Half-sandwich cyclopentandienyl molybdenum and tungsten nitrosyl complexes containing bidentate sulfur ligands

Half-sandwich nitrosyl complexes Cp*M(NO)I-2 (M = Mo, or W) react with dithiocarbamates (NaS2CNMe2 and NaS2CNEt2) in THF to form of complexes: Cp*Mo(NO)I (S2CNMe2) (1), Cp*Mo(NO)I(S2CNEt2) (2), Cp*W(NO)I(S2CNMe2) (3) and Cp*W(NO)I(S2CNEt2) (4) in high yields. Treatments of Cp*M(NO)I-2 (M = Mo, W) or [CpMo(NO)I-2](2) with phosphinodithioate (NaS2PMe2) and phosphorodithioate [(NH4)S2P(OMe)(2)] result in complexes: Cp*Mo(NO)I(S2PMe2) (5a), CpMo(NO)I (S2PMe2) (5b), Cp*Mo(NO)(S2PMe2)(2) (6a), CpMo (NO) (S2PMe2)(2) (6b) and Cp*Mo(NO)I[S2P(OMe)(2)] (7), Cp*W(NO)I(S2PMe2) (8), Cp*W(NO) I[S2P(OMe)](2) (9). Treatment of (5a) and (5b) with an excess of NaS2PMe2 gives (6a) and (6b). The complexes have been characterized by their elemental analyses, i.r., H-1, C-13-n.m.r. and by EI-MS spectrometry.

The use of half-sandwich iridium dithiolate and diselenolate complexes, Cp*Ir(L)(ER)(2) (L = CO, PMe3, PPh3; ER = SPh, SePh, SeMe), for the synthesis of heterodimetallic compounds. The molecular structure of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)]

Carbonyl-iridium half-sandwich compounds, Cp*Ir(CO)(EPh)(2) (E = S, Se), were prepared by the photo-induced reaction of Cp*Ir(CO)(2) with the diphenyl dichalcogenides, E2Ph2, and used as neutral chelating ligands in carbonylmetal complexes such as Cp*Ir(CO)(mu-EPh)(2)[Cr(CO)(4)], Cp*Ir(CO)(mu-EPh)(2)[Mo(CO)(4)] and Cp*Ir(CO)(mu-EPh)(2)[Fe(CO)(3)], respectively. A trimethylphosphane - iridium analogue, Cp*Ir(PMe3)(mu-SeMe)(2)[Cr(CO)(4)], was also obtained. The new heterodimetallic complexes were characterized by IR and NMR spectroscopy, and the molecular geometry of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)] has been determined by a single crystal X-ray structure analysis. According to the long Ir...Mo distance (395.3(1) Angstrom), direct metal-metal interactions appear to be absent. (C) 1998 Elsevier Science S.A. All rights reserved.

STRUCTURE-PROPERTY RELATIONSHIP BETWEEN HALF-WAVE POTENTIALS OF ORGANIC-COMPOUNDS AND THEIR TOPOLOGY

A significant correlation was found between half-wave potentials of organic compounds and their topological indices, A(x1), A(x2), and A(x3). The simplicity of calculation of the index from the connectivity in the molecular skeleton, together with the significant correlation, indicates its practical value. Good results have been obtained by using them to predict the half-wave potentials of some organic compounds.

PREPARATION AND STRUCTURE OF HALF-OPEN VANADOCENE, V[2,4-(CH3)2C5H5](C5H5)CO

The half-open vanadocene, V[2,4-(CH3)2C5H5](C5H5)CO, was obtained by the reaction of V[2,4-(CH3)2C5H5](C5H5)PMe3 with CO in petroleum ether at room temperature. Its crystal structure was determined by X-ray diffraction technique. The crystal was monoclinic with space group P2(1)/n, a = 16.614(3), b = 7.636(1), c = 19.128(6) angstrom, beta = 99.92(2)-degrees, V = 2390.5(9) angstrom3, and Z = 8. The final R value was 0.043. The V(1)-CPD(1) (half) (PD = 2,4-(CH3)2C5H5) bonds were shorter (0.038 angstrom) than the V(1)-CCP(1) (half) (CP = C5H5) bonds, averaging 2.224(4) versus 2.262(4) angstrom, respectively. 4V[2,4-(CH3)2C5H5](C5H5)CO has been characterized by IR and EPR methods.

Confidence intervals for half-life deviations from purchasing power parity

Existing point estimates of half-life deviations from purchasing power parity (PPP), around 3-5 years, suggest that the speed of convergence is extremely slow. This article assesses the degree of uncertainty around these point estimates by using local-to-unity asymptotic theory to construct confidence intervals that are robust to high persistence in small samples. The empirical evidence suggests that the lower bound of the confidence interval is between four and eight quarters for most currencies, which is not inconsistent with traditional price-stickiness explanations. However, the upper bounds are infinity for all currencies, so we cannot provide conclusive evidence in favor of PPP either. © 2005 American Statistical Association.

Mapping 2-D defects in a conductive half-space by eigenfunction expansions in K-space of Fourier-Laplace transforms

info:eu-repo/semantics/published

Study of the thermal stress in a Pb-free half-bump solder joint under current stressing

The thermal stress in a Sn3.5Ag1Cu half-bump solder joint under a 3.82×108 A/m2 current stressing was analyzed using a coupled-field simulation. Substantial thermal stress accumulated around the Al-to-solder interface, especially in the Ni+(Ni,Cu)3Sn4 layer, where a maximal stress of 138 MPa was identified. The stress gradient in the Ni layer was about 1.67×1013 Pa/m, resulting in a stress migration force of 1.82×10-16 N, which is comparable to the electromigration force, 2.82×10-16 N. Dissolution of the Ni+(Ni,Cu)3Sn4 layer, void formation with cracks at the anode side, and extrusions at the cathode side were observed

From silk to satellite: half a century of ocean colour anomalies in the Northeast Atlantic

Changes in phytoplankton dynamics influence marine biogeochemical cycles, climate processes, and food webs, with substantial social and economic consequences. Large-scale estimation of phytoplankton biomass was possible via ocean colour measurements from two remote sensing satellites – the Coastal Zone Color Scanner (CZCS, 1979-1986) and the Sea-viewing Wide Field-of-view Sensor (SeaWiFS, 1998-2010). Due to the large gap between the two satellite eras and differences in sensor characteristics, comparison of the absolute values retrieved from the two instruments remains challenging. Using a unique in situ ocean colour dataset that spans more than half a century, the two satellite-derived chlorophyll-a (Chl-a) eras are linked to assess concurrent changes in phytoplankton variability and bloom timing over the Northeast Atlantic Ocean and North Sea. Results from this unique re-analysis reflect a clear increasing pattern of Chl-a, a merging of the two seasonal phytoplankton blooms producing a longer growing season and higher seasonal biomass, since the mid-1980s. The broader climate plays a key role in Chl-a variability as the ocean colour anomalies parallel the oscillations of the Northern Hemisphere Temperature (NHT) since 1948.

There are no whole truths in meta-analyses: all their truths are half truths

In a recent letter, Thomsen & Wernberg (2015) rean-alyzed data compiled for our recent paper (Lyonset al., 2014). In that paper, we examined the effectsof macroalgal blooms and macroalgal mats on sevenimportant measures of community structure and eco-system functioning and explored several ecologicaland methodological factors that might explain someof the variation in the observed effects. Thomsen &Wernberg (2015) re-analyzed two small subsets of the data, focusing on experimental studies examining effects of blooms/mats on invertebrate abundance.Their analyses revealed two interesting patterns.First, they showed that macroalgal blooms reducedthe abundance of communities that Thomsen andWernberg categorized as ‘mainly infauna’, whileincreasing the abundance of communities categorized as ‘mainly epifauna’. Second, they showed that theimpacts of macroalgal blooms on ‘mainly infauna’communities increased with algal density in experiments that included multiple levels of algal density.These findings, as well as the conclusions that Thomsen & Wernberg (2015) draw from them, are largely consistent with our own expectations and interpretations. However, we also feel that some caution is required when interpreting the results of their analyses.

The Galactic metallicity gradient

We have previously published intermediate to hi,oh resolution spectroscopic observations of approximately 80 early B-type main-sequence stars situated in 19 Galactic open clusters/associations with Galactocentric distances distributed over 6 less than or equal to R-g less than or equal to 18 kpc. This current study collates and re-analyses these equivalent- width datasets using LTE and non-LTE model atmosphere techniques, in order to determine the stellar atmospheric parameters and abundance estimates for C, N, O, Mg, Al and Si. The latter should be representative of the present-day Galactic interstellar medium. Our extensive observational dataset permits the identification of sub-samples of stars with similar atmospheric parameters and of homogeneous subsets of lines. As such, this investigation represents the most extensive and systematic study of its kind to date. We conclude that the distribution of light elements (CI O, Mg & Si) in the Galactic disk can be represented by a linear, radial gradient of -0.07 +/- 0.01 dex kpc(-1) Our results for nitrogen and oxygen viz. (-0.09 +/- 0.01 dex kpc(-1) and -0.067 +/- 0.008 dex kpc(-1)) are in excellent agreement with that found from the study of HII regions. We have also examined our datasets for evidence of an abrupt discontinuity in the metallicity of the Galactic disk near a Galactocentric distance of 10 kpc (see Twarog et al. 1997). However, there is no evidence to suggest that our data would be better fitted with a two-zone model. Moreover, we observe a N/O gradient of -0.04 +/- 0.02 dex kpc(-1) which is consistent with that found for other spiral galaxies (Vila- Costas gr Edmunds 1993).

Understanding B-type supergiants in the low metallicity environment of the SMC

Spectroscopic analyses of 7 SMC B-type supergiants and 1 giant have been undertaken using high resolution optical data obtained on the VLT with UVES. FASTWIND, a non-LTE, spherical, line-blanketed model atmosphere code was used to derive atmospheric and wind parameters of these stars as well as their absolute abundances. Mass-loss rates, derived from H-alpha profiles, are in poor agreement with metallicity dependent theoretical predictions. Indeed the wind-momenta of the SMC stars appear to be in good agreement with the wind-momentum luminosity relationship (WLR) of Galactic B-type stars, a puzzling result given that line-driven wind theory predicts a metallicity dependence. However the galactic stars were analysed using unblanketed model atmospheres which may mask any dependence on metallicity. A mean nitrogen enhancement of a factor of 14 is observed in the supergiants whilst only an enrichment of a factor of 4 is present in the giant, AV216. Similar excesses in nitrogen are observed in O-type dwarfs and supergiants in the same mass range, suggesting that the additional nitrogen is produced while the stars are still on the main-sequence. These nitrogen enrichments can be reproduced by current stellar evolution models, which include rotationally induced mixing, only if large initial rotational velocities of 300 kin s(-1) are invoked. Such large rotational velocities appear to be inconsistent with observed v sin i distributions for O-type stars and B-type supergiants. Hence it is suggested that the currently available stellar evolution models require more efficient mixing for lower rotational velocities.