Mononuclear palladium and heterodinuclear palladium–ruthenium complexes of semicarbazone ligands: synthesis, characterization, and application in C–C cross-coupling reactions

Reaction of salicylaldehyde semicarbazone (L-1), 2-hydroxyacetophenone semicarbazone (L-2), and 2-hydroxynaphthaldehyde semicarbazone (L-3) with [Pd(PPh3)(2)Cl-2] in ethanol in the presence of a base (NEt3) affords a family of yellow complexes (1a, 1b and 1c, respectively). In these complexes the semicarbazone ligands are coordinated to palladium in a rather unusual tridentate ONN-mode, and a PPh3 also remains coordinated to the metal center. Crystal structures of the 1b and 1c complexes have been determined, and structure of 1a has been optimized by a DFT method. In these complexes two potential donor sites of the coordinated semicarbazone, viz. the hydrazinic nitrogen and carbonylic oxygen, remain unutilized. Further reaction of these palladium complexes (1a, 1b and 1c) with [Ru(PPh3)(2)(CO)(2)Cl-2] yields a family of orange complexes (2a, 2b and 2c, respectively). In these heterodinuclear (Pd-Ru) complexes, the hydrazinic nitrogen (via dissociation of the N-H proton) and the carbonylic oxygen from the palladium-containing fragment bind to the ruthenium center by displacing a chloride and a carbonyl. Crystal structures of 2a and 2c have been determined, and the structure of 2b has been optimized by a DFT method. All the complexes show characteristic H-1 NMR spectra and, intense absorptions in the visible and ultraviolet region. Cyclic voltammetry on all the complexes shows an irreversible oxidation of the coordinated semicarbazone within 0.86-0.93 V vs. SCE, and an irreversible reduction of the same ligand within -0.96 to -1.14 V vs. SCE. Both the mononuclear (1a, 1b and 1c) and heterodinuclear (2a, 2b and 2c) complexes are found to efficiently catalyze Suzuki, Heck and Sonogashira type C-C coupling reactions utilizing a variety of aryl bromides and aryl chlorides. The Pd-Ru complexes (2a, 2b and 2c) are found to be better catalysts than the Pd complexes (1a, 1b and 1c) for Suzuki and Heck coupling reactions.

Effect of anionic co-ligands on structure and magnetic coupling of bis(μ-phenoxo-bridged dinuclear copper(II) complexes

Two phenoxo bridged dinuclear Cu(II) complexes, [Cu2L2(NO2)(2)] (1) and [Cu2L2(NO3)(2)] (2) have been synthesized using the tridentate reduced Schiff-base ligand 2-[(2-dimethylamino-ethylamino)-methyl]-phenol (HL). The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The structures of the two compounds are very similar having the same tridentate chelating ligand (L) and mono-dentate anionic ligand nitrite for 1 and nitrate for 2. In both complexes Cu(II) is penta-coordinated but the square pyramidal geometry of the copper ions is severely distorted (Addison parameter (tau) = 0.33) in 1 while the distortion is quite small (average tau = 0.11) in 2. These differences have marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -140.8 and -614.7 cm (1) for 1 and 2, respectively) show that the coupling is much stronger in 2.

Syntheses, structures and efficient catalysis for C–C coupling of some benzaldehyde thiosemicarbazone complexes of palladium

Reaction of the 4-R-benzaldehyde thiosemicarbazones (denoted in general as L-R; R = OCH(3), CH(3), H, Cl and NO(2)) with trans-[Pd(PPh(3))(2)Cl(2)] afforded a group of mixed-ligand complexes (denoted in general as 1-R) incorporating a N,S-coordinated thiosemicarbazone. a triphenylphosphine and a chloride. Similar reaction with Na(2)[PdCl(4)] afforded a family of bis-thiosemicarbazone complexes (denoted in general as 2-R), where each ligand is N,S-coordinated. Crystal structures of 1-CH(3), 1-NO(2), 2-OCH(3), 2-NO(2) and L-NO(2) have been determined. In all the complexes the thiosemicarbazones are coordinated to the metal center, via dissociation of the acidic proton, as bidentate N,S-donors forming five-membered chelate rings. With reference to the structure of the uncoordinated thiosemicarbazone, this coordination mode is associated with a conformational change around the C=N bond. All the 1-R and 2-R complexes display intense absorptions in the visible region. Catalytic activity of the 1-R and 2-R complexes towards some C-C coupling reactions (e.g. Suzuki, Heck and Sonogashira) has been examined and while both are found to be efficient catalysts, 1-R is much better catalyst than 2-R.

Agency of Noise

Agency of Noise is a network of artists, musicians and academics from across the UK whose work is concerned with noise. The website offers a site for the development of online profiles for its members, the publication of works by members and the promotion and documentation of events hosted by the network. It also provides related links and references. The platform has developed from participation at national network events and conferences including Noise Vs Culture, University of Kent (2012); Liveness, University of Bournemouth (2012); Noise, Affect Politics, University of Salford (2010); and a research residency at The Banff Centre, Banff, Canada (2009).

The Prophetic Sound: a day and night of noise cabaret(symposium of talks and live performances)

'The Prophetic Sound: a day and night of noise cabaret' is the first event hosted by Agency of Noise. This all day event brought together artists and academics whose subject of focus is noise (in creative practice). Artists from across the UK were invited to consider a future post-digital era in which everything with a microchip has malfunctioned, as a thought exercise and starting point for response through sound. In response to Jacques Attali’s claim that music is prophecy, The Prophetic Sound asks us to consider if noise can communicate in an unbridled, unfiltered, way that is somehow not culturally coded -before it becomes sound that is recognised, refined, manipulated and exploited for musical or other cultured purpose. Featuring students from Reading, Brighton, LCC and Goldsmiths alongside more established artists and academics from across the UK, this event brings into focus locations where pattern, timbre, pitch, organisation and sequencing of sounds become distinguishable from noise and asks us to consider, through diversion within such locations, new origins for future communication systems. The Prophetic Sound included talks, films, presentations and performances from: Ryo Ikeshiro / Inigo Wilkins / Neal Spowage / Dane Sutherland / Poulomi Desai / Benedict Drew / AAS / Polly Fibre / Steven Dickie As part of The Prophetic Sound, POLLYFIBRE (Ellison, C.) performed LIVE RECORDING with Amplified Scissors. This industrial activity by POLLYFIBRE short-circuits the complicated chain that is music production. The distinctive roles of consumer, producer, composer, and performer collapse in a series of live ‘cuts’ where vinyl discs are produced with amplified scissors. Production happens through action and action becomes production. A limited edition of 9 flexi discs were produced and available for special collectors at the event.

Recent advances in global electric circuit coupling between the space environment and the troposphere

The global atmospheric electric circuit is driven by thunderstorms and electrified rain/shower clouds and is also influenced by energetic charged particles from space. The global circuit maintains the ionosphere as an equipotential at∼+250 kV with respect to the good conducting Earth (both land and oceans). Its “load” is the fair weather atmosphere and semi-fair weather atmosphere at large distances from the disturbed weather “generator” regions. The main solar-terrestrial (or space weather) influence on the global circuit arises from spatially and temporally varying fluxes of galactic cosmic rays (GCRs) and energetic electrons precipitating from the magnetosphere. All components of the circuit exhibit much variability in both space and time. Global circuit variations between solar maximum and solar minimum are considered together with Forbush decrease and solar flare effects. The variability in ion concentration and vertical current flow are considered in terms of radiative effects in the troposphere, through infra-red absorption, and cloud effects, in particular possible cloud microphysical effects from charging at layer cloud edges. The paper identifies future research areas in relation to Task Group 4 of the Climate and Weather of the Sun-Earth System (CAWSES-II) programme.

One-port de-embedding technique for the quasi-optical characterization of integrated components

We describe a one-port de-embedding technique suitable for the quasi-optical characterization of terahertz integrated components at frequencies beyond the operational range of most vector network analyzers. This technique is also suitable when the manufacturing of precision terminations to sufficiently fine tolerances for the application of a TRL de-embedding technique is not possible. The technique is based on vector reflection measurements of a series of easily realizable test pieces. A theoretical analysis is presented for the precision of the technique when implemented using a quasi-optical null-balanced bridge reflectometer. The analysis takes into account quantization effects in the linear and angular encoders associated with the balancing procedure, as well as source power and detector noise equivalent power. The precision in measuring waveguide characteristic impedance and attenuation using this de-embedding technique is further analyzed after taking into account changes in the power coupled due to axial, rotational, and lateral alignment errors between the device under test and the instruments' test port. The analysis is based on the propagation of errors after assuming imperfect coupling of two fundamental Gaussian beams. The required precision in repositioning the samples at the instruments' test-port is discussed. Quasi-optical measurements using the de-embedding process for a WR-8 adjustable precision short at 125 GHz are presented. The de-embedding methodology may be extended to allow the determination of S-parameters of arbitrary two-port junctions. The measurement technique proposed should prove most useful above 325 GHz where there is a lack of measurement standards.

Stratosphere‐troposphere coupling and annular mode variability in chemistry‐climate models

The internal variability and coupling between the stratosphere and troposphere in CCMVal‐2 chemistry‐climate models are evaluated through analysis of the annular mode patterns of variability. Computation of the annular modes in long data sets with secular trends requires refinement of the standard definition of the annular mode, and a more robust procedure that allows for slowly varying trends is established and verified. The spatial and temporal structure of the models’ annular modes is then compared with that of reanalyses. As a whole, the models capture the key features of observed intraseasonal variability, including the sharp vertical gradients in structure between stratosphere and troposphere, the asymmetries in the seasonal cycle between the Northern and Southern hemispheres, and the coupling between the polar stratospheric vortices and tropospheric midlatitude jets. It is also found that the annular mode variability changes little in time throughout simulations of the 21st century. There are, however, both common biases and significant differences in performance in the models. In the troposphere, the annular mode in models is generally too persistent, particularly in the Southern Hemisphere summer, a bias similar to that found in CMIP3 coupled climate models. In the stratosphere, the periods of peak variance and coupling with the troposphere are delayed by about a month in both hemispheres. The relationship between increased variability of the stratosphere and increased persistence in the troposphere suggests that some tropospheric biases may be related to stratospheric biases and that a well‐simulated stratosphere can improve simulation of tropospheric intraseasonal variability.

Issues in stratosphere-troposphere coupling

An overview is given of current issues concerning the coupling between the stratosphere and troposphere. The tropopause region, more generally the upper troposphere/lower stratosphere, is the region of direct contact where exchange of material takes place. Dynamical coupling through angular momentum transfer by waves occurs nonlocally, and provides a generally negative torque on the stratosphere which drives an equator-to-pole circulation (i.e., towards the Earth’s axis of rotation). This wave-driven circulation is the principal mechanism for intraseasonal and interannual variability in the extratropical stratosphere. Although such variability is generally dynamical in origin, there are important chemical and radiative feedbacks. The location of the tropopause has implications for radiative forcing of climate, through its effect on the distribution of relatively short-lived greenhouse gases (ozone and water vapour). Some outstanding puzzles in our current understanding are identified. Attention is focused on possible climate sensitivities, and how these may be tested and constrained. Results from the Canadian Middle Atmosphere Model (CMAM), a fully interactive radiative-chemical-dynamical general circulation model, are used to illustrate some of the points.

Noise propagation from a cutting of arbitrary cross-section and impedance

A boundary integral equation is described for the prediction of acoustic propagation from a monofrequency coherent line source in a cutting with impedance boundary conditions onto surrounding flat impedance ground. The problem is stated as a boundary value problem for the Helmholtz equation and is subsequently reformulated as a system of boundary integral equations via Green's theorem. It is shown that the integral equation formulation has a unique solution at all wavenumbers. The numerical solution of the coupled boundary integral equations by a simple boundary element method is then described. The convergence of the numerical scheme is demonstrated experimentally. Predictions of A-weighted excess attenuation for a traffic noise spectrum are made illustrating the effects of varying the depth of the cutting and the absorbency of the surrounding ground surface.

The combined effects of porous asphalt surfacing and barriers on traffic noise

There is considerable interest in the use of porous asphalt (PA) surfacing on highways since physical and subjective assessments of noise have indicated a significant advantage over conventional non-porous surfaces such as hot rolled asphalt (HRA) used widely for motorway surfacing in the UK. However, it was not known whether the benefit of the PA surface was affected by the presence of roadside barriers. Noise predictions have been made using the Boundary Element Method (BEM) approach to determine the extent to which the noise reducing benefits of PA could be added to the screening effects of noise barriers in order to obtain the overall reduction in noise levels

Influence of shape and absorbing surface: a numerical study of railway noise barriers

Results are presented of a study of a performance of various track-side railway noise barriers, determined by using a two- dimensional numerical boundary element model. The basic model uses monopole sources and has been adapted to allow the sources to exhibit dipole-type radiation characteristics. A comparison of boundary element predictions of the performance of simple barriers and vehicle shapes is made with results obtained by using the standard U.K. prediction method. The results obtained from the numerical model indicate that modifying the source to exhibit dipole characteristics becomes more significant as the height of the barrier increases, and suggest that for any particular shape, absorbent barriers provide much better screening efficiency than the rigid equivalent. The cross-section of the rolling stock significantly affects the performance of rigid barriers. If the position of the upper edge is fixed, the results suggest that simple absorptive barriers provide more effective screening than tilted barriers. The addition of multiple edges to a barrier provides additional insertion loss without any increase in barrier height.

Multiple-edge noise barriers

A numerical model using boundary element techniques is discussed which enables the insertion loss for various noise barriers of complex profile and surface cover to be calculated. The model is applied to single-foundation noise barriers to which additional side-panels are added to create fork-like profiles. Spectra of insertion loss and mean insertion loss results over a range of receiver positions for a broadband source are presented. It is concluded that ‘multiple-edged’ barriers show a significant increase in acoustic-efficiency over a simple vertical screen. Adding lightweight side-panels would be a relatively inexpensive measure, and one which could be applied to barriers already in existence. This type of barrier would also allow the height of the construction to be kept to a minimum.

The simulation of the opposing fluxes of latent heat and CO2 over various land-use types: coupling a gas exchange model to a mesoscale atmospheric model

A mesoscale meteorological model (FOOT3DK) is coupled with a gas exchange model to simulate surface fluxes of CO2 and H2O under field conditions. The gas exchange model consists of a C3 single leaf photosynthesis sub-model and an extended big leaf (sun/shade) sub-model that divides the canopy into sunlit and shaded fractions. Simulated CO2 fluxes of the stand-alone version of the gas exchange model correspond well to eddy-covariance measurements at a test site in a rural area in the west of Germany. The coupled FOOT3DK/gas exchange model is validated for the diurnal cycle at singular grid points, and delivers realistic fluxes with respect to their order of magnitude and to the general daily course. Compared to the Jarvis-based big leaf scheme, simulations of latent heat fluxes with a photosynthesis-based scheme for stomatal conductance are more realistic. As expected, flux averages are strongly influenced by the underlying land cover. While the simulated net ecosystem exchange is highly correlated with leaf area index, this correlation is much weaker for the latent heat flux. Photosynthetic CO2 uptake is associated with transpirational water loss via the stomata, and the resulting opposing surface fluxes of CO2 and H2O are reproduced with the model approach. Over vegetated surfaces it is shown that the coupling of a photosynthesis-based gas exchange model with the land-surface scheme of a mesoscale model results in more realistic simulated latent heat fluxes.