Oxidative addition of (PhSe)2 and (FcSe)2 to zerovalent palladium and platinum trialkylphosphine complexes (Fc = ferrocenyl, [Fe(η-C5H5)(η-C5H4)])

Room temperature reaction of [Pd₂(dba)₃]/PR₃ or [Pt(C₂H₄)(PR₃)₂] (dba = dibenzylideneacetone; R = Et, Bu) with the diselenides (R′Se)₂ (R′ = Ph, Fc) yielded the oxidative addition products trans-[M(SeR′)₂(PR₃)₂] (M = Pd, Pt). These have been characterised by multinuclear NMR and UV-Vis spectroscopy, mass spectrometry, and, in the cases of trans-[Pt(SePh)₂(PR₃)₂] (R = Et, Bu) and trans-[Pt(SeFc)₂(PBu₃)₂], also by X-ray crystallography.     

Exact one-sided simultaneous confidence bands via Uusipaikka’s method

Computation of one-sided simultaneous confidence bands is detailed for a simple linear regression under interval restrictions on the predictor variable, using a method due to Uusipaikka (1983,J. Amer. Statist. Assoc.,78, 638–644). The case of a single interval restriction is emphasized. A WWW-based applet for computing the bands is described.     

The effect of bed roughness on scalar fluctuations in turbulent boundary layers

The effect of bed roughness on an iso-kinetic chemical plume released into the logarithmic region of the bed boundary layer of an open channel flow is examined. The bed roughness is varied systematically to generate flows in the smooth (painted polyethylene sheets), transitional rough (2.5-mm and 11.5-mm gravel beds), and fully rough (21.0-mm gravel bed) regimes. Concentration fields are measured in horizontal planes using the planar laser-induced fluorescence (PLIF) technique. The time-averaged concentration follows a self-similar Gaussian transverse profile for each bed roughness. The plume width grows as a power law function of the streamwise distance (i.e., with n0.75 near the source and n0.5 farther downstream). As the bed roughness increases, the variance of the fluctuations is smaller and decreases faster. Near the plume source, the transverse profiles of the standard deviation of the scalar fluctuations are self-similar and Gaussian. For the two rougher beds, the transverse distribution of the standard deviation transitions downstream to a bi-modal profile. The probability density functions (PDFs) of the concentration fluctuations near the plume source are highly skewed distributions. Increased bed roughness accelerates the approach of the PDF towards a Gaussian distribution.     

Experimental and computational evidence for a boron-assisted,sigma-bond metathesis pathway for alkane borylation

Photoejection of one CO ligand from isolated CpM(CO)n+1BR2 (n = 1: M = Fe, Ru; n = 2: M = Mo,W; R2 = catecholate or pinacolate) compounds produces a coordinatively unsaturated 16 e- intermediate, a cyclic dioxaboryl transition metal complex, that can efficiently and selectively initiate regioselective C-H bond activation and can be used in the functionalization of alkanes. This chemistry appears distinct from that reported previously for related CpM(CO)n complexes of alkyl and aryl ligands. We show here by a combination of experimental and theoretical studies that the "unoccupied" p orbital of dioxaboryl ligands are intimately involved in the C-H bond activation step and that this hydrogen transfer to boron occurs by a boron-assisted, metal-mediated sigma-bond metathesis. The "unoccupied" p orbital of boron lowers the energy of the transition state and the intermediates by accepting electron density from the metal. The metal-bound borane then rotates, transfers back through a sigma-bond metathesis to capture the alkyl, and leaves the metal hydride.     

Background light measurements in the deep ocean

Summary Ambient light intensities in the ocean at depths between 1500 m and 4700 m near Hawaii Island were measured around the one photoelectron level with 5″ diameter hemispherical photomultipliers. Measurements of count rates above variable thresholds were carried out in ship-suspended and bottom-tethered configurations. The ship-suspended rates show considerable fluctuation and their mean value decreases with depth approximately as exp [−x(m)/877]. The bottomtethered rates are about an order of magnitude lower than the ship-suspended rates and show little fluctuation. The calibration of our instrument indicates an absolute flux at 4700 m depth based on the bottom-tethered measurement of 218 ₋₆₀ ⁺²⁰ photons/cm²·s, which is consistent with calculated intensities due to β-decay electrons from⁴⁰K. The difference in the two cases is attributed to bioluminescence due to environmental stimulation.

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Riassunto Sono state misurate le intensità di luce ambiente nell'oceano a profondità tra 1500 m e 4700 m vicino alle isole Hawaii intorno al livello ad un fotoelettrone con fotomoltiplicatori emisferici di 5″ di diametro. Sono state effettuate le misure delle frequenze di conteggio oltre alle soglie delle variabili in configurazioni appese alla nave e ancorate al fondo. Le frequenze delle configurazioni appese alla nave mostrano una fluttuazione considerevole e il loro valore medio decresce con la profondità come exp [−x(m)/877]. Le frequenze delle configurazioni ancorate al fondo sono circa di un ordine di grandezza inferiore di quelle delle configurazioni appese alla nave e mostrano una piccola fluttuazione. La calibrazione del nostro strumento indica un flusso assoluto a 4700 m di profondità basato sulla misura delle configurazioni ancorate al fondo di 218 ₋₆₀ ⁺²⁰ fotoni/cm²·s, che è consistente con le intensità calcolate dovute al decadimento β degli elettroni da⁴⁰K. Si attribuisce la differenza nei due casi alla bioluminescenza dovuta alla stimolazione ambientale.

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Резюме Измеряются интенсивности свечения окружающей среды в океане на глубинах от 1500 м до 4700 м вблизи Гавайских островов с помощью 5-дюймовых полусферических фотоумножителей. йзмерения скоростей счета выше изменяющихся порогов были проведены в случае подвешенном на корабле и в случае прикрелления ко дну. Интенсивности счета в подвешенном состояиии обнаруживают значительные флуктуации и их средняя величина уменьшается с глубиной приблизительно как ехп [−x(m)/877]. Интенсивности счета в случае прикрепления ко дну примерно на порядок меньше интенсивностей в подвешенном состоянии и обнаруживаут малые флуктуации. Градуировка нашей аппаратуры даст на основе измерений в случае прикрепления ко дну величину абсолутного потока на глубине 4700 м, равную 218 ₋₆₀ ⁺²⁰ фотонов/см² с, которая согласуется с вычисленными интенсивностями, обусловленными электронами β-распада от⁴⁰К. Различия, обнаруженные в двух случаях, приписываются биолюминесценции, связанной с возбуждением окружающеи среды.

     

Chemical order and magnetic properties of the Ni2−xMnSb system

The results of extensive magnetisation, X-ray and neutron powder diffraction measurements on the intermetallic compound series Ni_2-xMnSb, for 0?x?1, are reported. For x ?0.4, a high degree in the C1_b structure is observed, but for x?0.3, some disorder is evident. The series is ferromagnetic, with Curie temperatures rising from 368 to 732 K with decreasing nickel concentration. The magnetic moments all lie in the range (4.0±0.3)μ_B, with a maximum at a composition near x=0.45. The magnetic moments are largely associated with the ordered manganese sites, but it is possible that a small negative moment ?0.25μ_B may be associated with the “nickel sites” for x?0.3. This latter moment may be accounted for by disordered Mn atoms antiferromagnetically aligned.