Nickel complexes of phosphine-appended benzannulated boron heterocycles

We report the synthesis and characterization of two diphosphine nickel complexes containing 9-borafluorene (PBFlu, 9-(diisopropylphosphino)phenyl-9-borafluorene) and 9,10-dihydroboranthrene (B 2 P 2 , 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) cores. Metalation of PBFlu and B 2 P 2 with Ni(PPh 3 ) 4 leads to the monometallic complexes (PBFlu)Ni(PPh 3 ) and (B 2 P 2 )Ni, respectively. Cyclic voltammetry studies show a reversible redox event at ∼0.1 V and a quasi-reversible event at ca. −3 V versus ferrocene/ferrocenium for (B 2 P 2 )Ni while (PBFlu)Ni(PPh 3 ) features no reversible redox events. Electronic structure calculations were performed to provide further insight into the bonding in these complexes

CO2 reduction with protons and electrons at a boron-based reaction center.

Borohydrides are widely used reducing agents in chemical synthesis and have emerging energy applications as hydrogen storage materials and reagents for the reduction of CO2. Unfortunately, the high energy cost associated with the multistep preparation of borohydrides starting from alkali metals precludes large scale implementation of these latter uses. One potential solution to this issue is the direct synthesis of borohydrides from the protonation of reduced boron compounds. We herein report reactions of the redox series [Au(B2P2)] n (n = +1, 0, -1) (B2P2, 9,10-bis(2-(diisopropylphosphino)phenyl)-9,10-dihydroboranthrene) and their conversion into corresponding mono- and diborohydride complexes. Crucially, the monoborohydride can be accessed via protonation of [Au(B2P2)]-, a masked borane dianion equivalent accessible at relatively mild potentials (-2.05 V vs. Fc/Fc+). This species reduces CO2 to produce the corresponding formate complex. Cleavage of the formate complex can be achieved by reduction (ca. -1.7 V vs. Fc/Fc+) or by the addition of electrophiles including H+. Additionally, direct reaction of [Au(B2P2)]- with CO2 results in reductive disproportion to release CO and generate a carbonate complex. Together, these reactions constitute a synthetic cycle for CO2 reduction at a boron-based reaction center that proceeds through a B-H unit generated via protonation of a reduced borane with weak organic acids

Editorial : Poverty and mobility in England, 1600–1850

Within these pages you will find a ‘jovial crew’: rogues and vagabonds, the ‘mad’ and insane, gypsies, peddlers, poets, playwrights, pilgrims, rioters, convicts, constables, thieves, beggars, landed gentlemen, magistrates, and historians. When parliamentarians and projectors set out to proscribe mobility and legislate poverty in early modernity, a list of untrustworthy trades and professions not at all unlike this one frequently found its way into print and the statute book. The punishment for crimes of vagrancy could be severe, but thankfully ‘historians’ were not counted among the undeserving and mobile, nor would you find magistrates and landed gentlemen taken up, imprisoned, and whipped for a crime of movement. However, all three groups may well deserve some of John Locke's brand of draconian ‘improvement’; historians in particular have taken little account of the lived experiences of the mobile poor until relatively recently. Once we finally took a hard look at our inherited, literature-driven typologies of ‘rogues’ and ‘beggars’, they disappeared in ‘a storm of dust and lies.’ However, the literary, visualised vagabond still has much to tell us, and interdisciplinary approaches to vagrancy in the past have emerged as the strongest method yet of reconstructing the character, history, and cultural perception of the mobile poor. These are methods which the articles in this collection use to full effect

Optimum take-off angle in the standing long jump

The aim of this study was to identify and explain the optimum projection angle that maximises the distance achieved in a standing long jump. Five physically active males performed maximum-effort jumps over a wide range of take-off angles, and the jumps were recorded and analysed using a 2-D video analysis procedure. The total jump distance achieved was considered as the sum of three component distances (take-off, flight, and landing), and the dependence of each component distance on the take-off angle was systematically investigated. The flight distance was strongly affected by a decrease in the jumper’s take-off speed with increasing take-off angle, and the take-off distance and landing distance steadily decreased with increasing take-off angle due to changes in the jumper’s body configuration. The optimum take-off angle for the jumper was the angle at which the three component distances combined to produce the greatest jump distance. Although the calculated optimum take-off angles (19–27º) were lower than the jumpers’ preferred take-off angles (31–39º), the loss in jump distance through using a sub-optimum take-off angle was relatively small

Optimum take-off angle in the standing long jump

The aim of this study was to identify and explain the optimum projection angle that maximises the distance achieved in a standing long jump. Five physically active males performed maximum-effort jumps over a wide range of take-off angles, and the jumps were recorded and analysed using a 2-D video analysis procedure. The total jump distance achieved was considered as the sum of three component distances (take-off, flight, and landing), and the dependence of each component distance on the take-off angle was systematically investigated. The flight distance was strongly affected by a decrease in the jumper’s take-off speed with increasing take-off angle, and the take-off distance and landing distance steadily decreased with increasing take-off angle due to changes in the jumper’s body configuration. The optimum take-off angle for the jumper was the angle at which the three component distances combined to produce the greatest jump distance. Although the calculated optimum take-off angles (19–27º) were lower than the jumpers’ preferred take-off angles (31–39º), the loss in jump distance through using a sub-optimum take-off angle was relatively small

Hubble Space Telescope Imaging of the Expanding Nebular Remnant of the Recurrent Nova RS Ophiuchi (2006)

We report Hubble Space Telescope imaging obtained 155 days after the 2006 outburst of RS Ophiuchi. We detect extended emission in both [O III] and [Ne V] lines. In both lines, the remnant has a double ring structure. The E-W orientation and total extent of these structures (580+-50 AU at d=1.6kpc) is consistent with that expected due to expansion of emitting regions imaged earlier in the outburst at radio wavelengths. Expansion at high velocity appears to have been roughly constant in the E-W direction (v_{exp} = 3200+-300 km/s in the plane of the sky), with tentative evidence of deceleration N-S. We present a bipolar model of the remnant whose inclination is consistent with that of the central binary. The true expansion velocities of the polar components are then v = 5600+-1100 km/s. We suggest that the bipolar morphology of the remnant results from interaction of the outburst ejecta with a circumstellar medium that is significantly denser in the equatorial regions of the binary than at the poles. This is also consistent with observations of shock evolution in the X-ray and the possible presence of dust in the infrared. Furthermore, it is in line with models of the shaping of planetary nebulae with close binary central systems, and also with recent observations relating to the progenitors of Type Ia supernovae, for which recurrent novae are a proposed candidate. Our observations also reveal more extended structures to the S and E of the remnant whose possible origin is briefly discussed.Comment: 13 pages, 2 figures, accepted for publication in ApJ