Metal cluster expansion by addition of low-valent group 4B reagents: crystal and molecular structure of [Os3SnH2(CO)10{CH(SiMe3)2}2]; a compound with hydrogen bridging osmium and tin

Cluster expansion of [Os3H2(CO)10] with [SnR2][R = CH(SiMe3)2] take place in high yield to give [Os3SnH2(CO)10R2], the first closed triosmium–main-group metal cluster to be structurally characterized; a novel feature is the presence of a hydrogen atom bridging the tin atom and one of the osmium atoms.

Heterosite effects in novel heteronuclear clusters [OS2Ru(CO)(11)(PPh3)] and Os2Ru(CO)(10)(2-acetylpyridine-N-isopropylimine)]

A new synthetic route towards the mixed-metal cluster [OS2Ru(CO)(12)] is described together with the syntheses of its PPh3 and iPr-AcPy (iPr-AcPy = 2-acetylpyridine-N-isopropylimine) derivatives. The molecular structures of the novel clusters [Os2Ru(CO)(11)(PPh3)] and [Os2Ru(CO)(10)(iPr-AcPy)] were determined on the basis of crystalline solid solutions of the Os2Ru and corresponding Os-3 species. The structures reveal that coordination of the Lewis bases occurs exclusively at the ruthenium site of [Os2Ru(CO)(12)], which is in agreement with density functional theory (DFT) calculations on several structural isomers of these compounds. According to the time-dependent DFT results, the lowest optically accessible excited state of [Os2Ru(CO)(10)(iPr-AcPy)] has a prevailing sigma(Ru-Os-2)pi*(iPr-AcPy) character, with a partial sigma sigma*(Ru-Os-2) contribution. In weakly coordinating 2-chlorobutane, the excited state has a lifetime tau = 10.4 +/- 1.2 ps and produces biradicals considerably faster than observed for [Os-3(CO)10(iPr-AcPy) (tau = 25.3 +/- 0.7ps)]. In coordinating acetonitrile, the excited state of [Os2Ru(CO)(10)(iPr-AcPy)] decays mono-exponentially with a lifetime tau = 2.1 +/- 0.2 ps. In contrast to [Os-3(CO)(10)(iPr-AcPy)] that forms biradicals as the main primary photoproduct even in strongly coordinating solvents, zwitterion formation from the solvated lowest excited state is observed for the heterometallic cluster. This is concluded from time-resolved absorption studies in the microsecond time domain. Due to the lower tendency of the coordinatively unsaturated Ru+(CO)(2)(iPr-AcPy-/0) moiety to bind a Lewis base, the heteronuclear biradical and zwitterionic photoproducts live significantly shorter than their triosmium counterparts. The influence of the weaker Os-2-Ru(iPr-AcPy) bond on the redox reactivity is clearly reflected in very reactive radical anions formed upon electrochemical reduction of [Os2Ru(CO)(10)(iPr-AcPy)]. The dimer [-OS(CO)(4)-Os(CO)(4)-Ru(CO)(2)(iPr-AcPy)](2)(2-) is the only IR-detectable intermediate reduction product. The dinuclear complex [Os-2(CO)(8)](2-) and insoluble [Ru(CO)(2)(iPr-AcPy)](n), are the ultimate reduction products, proving fragmentation of the OS2Ru core.

Equilibrium studies on mixed ligand complex formation of Co(II), Ni(II), Cu(II) and Zn(II) with N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his) and typical N,N donor ligands: Crystal structure of [Ni(hb-L-his)(bipyridine)]center dot H2O complex

Equilibrium study on complex formation of Co(II), Ni(II), Cu(II) and Zn(II), hereafter M(II), with the quadridentate (O-, N, O-, N) donor ligand, N-(2-hydroxybenzyl)-L-histidine (H(2)hb-L-his, hereafter H2L), in the absence and in the presence of typical (N, N) donor bidentate ligands, 1,10 phenanthroline(phen), 2, 2'-bipyridine(bipy), ethylenediamine(en), hereafter B, in aqueous solution at 25 +/- 1 degrees C was done at a fixed ionic strength, I = 0.1 mol dm(-3) (NaNO3) by combined pH-metric, UV-Vis and EPR measurements provide evidence for the formation of mononuclear and dinuclear binary and mixed ligand complexes of the types: M(L), M(L)(2)(2-), M-2(L)(2+), M-2(H-1L)(+), M(L)(B), (B)M(H-1L)M(B)(+). The imidazole moiety of the ligand is found to act as a bridging bidentate ligand in the dinuclear M-2(L)(2+), M-2(H-1L)(+) and (B)M(H-1L)M(B)(+) complexes, using its N-3 atom and N1-H deprotonated moiety. Stability constants of the complexes provide evidence of discrimination of Cu(II) from the other M(II) ions by this ligand. Solid complexes: [Ni(L)(H2O)(2)] (1), [Cu(L)(H2O)] (2), and [Ni(L)(bipy)] (.) H2O (3) have been isolated and characterized by various physicochemical studies. Single crystal X-ray diffraction of the ternary complex, 3, shows an octahedral [(O-,N,N,O-)(N,N)] geometry with extensive pi-pi stacking of the aromatic rings and H-bonding with imidazole (N1-H), secondary amino N-atom, the lattice H2O molecule, and the carboxylate and phenolate O-atoms. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis, crystal structure, magnetic behavior and thermal property of three polynuclear complexes: [M(dca)(2)(H2O)2](n)center dot(hmt)(n) [M = Mn(II), Co(II)] and [Co(dca)(2)(bpds)](n) [dca, dicyanamide; hint, hexamethylenetetramine; bpds, 4,4 '-bipyridyl disulfide]

Three mu(1.5)-dicyanamide bridged Mn(II) and Co(II) complexes having molecular formula [Mn(dca)(2)(H2O)(2)](n)center dot(hmt)(n) (1), [Co(dca)(2) (H2O)(2)](n)center dot(hmt)(n) (2) and [Co(dca)(2)(bpds)](n) (3) [dca = dicyanamide; hmt = hexamethylenetetramine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and characterized by single crystal X-ray diffraction study, low temperature (300-2 K) magnetic measurement and thermal behavior. The X-ray diffraction analysis of 1 and 2 reveals that they are isostructural, comprising of 1D coordination polymers [M(dca)(2)(H2O)(2)](n) [M = Mn(II), Co(II) for 1 and 2. respectively] with uncoordinated hmt molecules located among the chains. The [M(dca)(2)(H2O)(2)](n) chains and the lattice hint molecules are connected through H-bonds resulting in a 3D supramolecular architecture. The octahedral N4O2 chromophore surrounding the metal ion forms via two trans located water oxygens and four nitrogens from four nitrile dca. Complex 3 is a 1D chain formed by two mu(1.5)-dca and one bridging bpds. The octahedral N-6 coordination sphere surrounding the cobalt ions comprises four nitrogens from dca and two from bpds. Low temperature magnetic study indicates small antiferromagnetic coupling for all the complexes. Best fit parameters for 1: J = -0.17 cm(-1), g = -2.03 with R = 6.1 x 10(-4), for 2, J = -0.50 cm(-1), and for 3, J = -0.95 cm(-1). (c) 2005 Elsevier B.V. All rights reserved.

Multistep electrochemical reduction path of clusters [Os3(CO)10(α-diimine)]: comparison of electrochemical and photochemical Os-Os(α-diimine) bond cleavage

Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Type 2 diabetes and impaired glucose tolerance are associated with word memory source monitoring recollection deficits but not simple recognition familiarity deficits following water, low glycaemic load, and high glycaemic load breakfasts.

Isolated source monitoring recollection deficits indicate that abnormalities in glucose metabolism are not detrimental for global episodic memory processes. This enhances our understanding of how metabolic disorders are associated with memory impairments.

A case study of boundary layer ventilation by convection and coastal processes

It is often assumed that ventilation of the atmospheric boundary layer is weak in the absence of fronts, but is this always true? In this paper we investigate the processes responsible for ventilation of the atmospheric boundary layer during a nonfrontal day that occurred on 9 May 2005 using the UK Met Office Unified Model. Pollution sources are represented by the constant emission of a passive tracer everywhere over land. The ventilation processes observed include shallow convection, turbulent mixing followed by large-scale ascent, a sea breeze circulation and coastal outflow. Vertical distributions of tracer are validated qualitatively with AMPEP (Aircraft Measurement of chemical Processing Export fluxes of Pollutants over the UK) CO aircraft measurements and are shown to agree impressively well. Budget calculations of tracers are performed in order to determine the relative importance of these ventilation processes. Coastal outflow and the sea breeze circulation were found to ventilate 26% of the boundary layer tracer by sunset of which 2% was above 2 km. A combination of coastal outflow, the sea breeze circulation, turbulent mixing and large-scale ascent ventilated 46% of the boundary layer tracer, of which 10% was above 2 km. Finally, coastal outflow, the sea breeze circulation, turbulent mixing, large-scale ascent and shallow convection together ventilated 52% of the tracer into the free troposphere, of which 26% was above 2 km. Hence this study shows that significant ventilation of the boundary layer can occur in the absence of fronts (and thus during high-pressure events). Turbulent mixing and convection processes can double the amount of pollution ventilated from the boundary layer.

Sampling uncertainties in surface radiation budget calculations in RADAGAST

In the Radiative Atmospheric Divergence Using ARM Mobile Facility GERB and AMMA Stations (RADAGAST) project we calculate the divergence of radiative flux across the atmosphere by comparing fluxes measured at each end of an atmospheric column above Niamey, in the African Sahel region. The combination of broadband flux measurements from geostationary orbit and the deployment for over 12 months of a comprehensive suite of active and passive instrumentation at the surface eliminates a number of sampling issues that could otherwise affect divergence calculations of this sort. However, one sampling issue that challenges the project is the fact that the surface flux data are essentially measurements made at a point, while the top-of-atmosphere values are taken over a solid angle that corresponds to an area at the surface of some 2500 km2. Variability of cloud cover and aerosol loading in the atmosphere mean that the downwelling fluxes, even when averaged over a day, will not be an exact match to the area-averaged value over that larger area, although we might expect that it is an unbiased estimate thereof. The heterogeneity of the surface, for example, fixed variations in albedo, further means that there is a likely systematic difference in the corresponding upwelling fluxes. In this paper we characterize and quantify this spatial sampling problem. We bound the root-mean-square error in the downwelling fluxes by exploiting a second set of surface flux measurements from a site that was run in parallel with the main deployment. The differences in the two sets of fluxes lead us to an upper bound to the sampling uncertainty, and their correlation leads to another which is probably optimistic as it requires certain other conditions to be met. For the upwelling fluxes we use data products from a number of satellite instruments to characterize the relevant heterogeneities and so estimate the systematic effects that arise from the flux measurements having to be taken at a single point. The sampling uncertainties vary with the season, being higher during the monsoon period. We find that the sampling errors for the daily average flux are small for the shortwave irradiance, generally less than 5 W m−2, under relatively clear skies, but these increase to about 10 W m−2 during the monsoon. For the upwelling fluxes, again taking daily averages, systematic errors are of order 10 W m−2 as a result of albedo variability. The uncertainty on the longwave component of the surface radiation budget is smaller than that on the shortwave component, in all conditions, but a bias of 4 W m−2 is calculated to exist in the surface leaving longwave flux.

Simulation of the Earth's radiation budget by the European Centre for Medium-Range Weather Forecasts 40-year reanalysis (ERA40)

The radiation budget simulated by the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year reanalysis (ERA40) is evaluated for the period 1979–2001 using independent satellite data and additional model data. This provides information on the quality of the radiation products and indirect evaluation of other aspects of the climate produced by ERA40. The climatology of clear-sky outgoing longwave radiation (OLR) is well captured by ERA40. Underestimations of about 10 W m−2 in clear-sky OLR over tropical convective regions by ERA40 compared to satellite data are substantially reduced when the satellite sampling is taken into account. The climatology of column-integrated water vapor is well simulated by ERA40 compared to satellite data over the ocean, indicating that the simulation of downward clear-sky longwave fluxes at the surface is likely to be good. Clear-sky absorbed solar radiation (ASR) and clear-sky OLR are overestimated by ERA40 over north Africa and high-latitude land regions. The observed interannual changes in low-latitude means are not well reproduced. Using ERA40 to analyze trends and climate feedbacks globally is therefore not recommended. The all-sky radiation budget is poorly simulated by ERA40. OLR is overestimated by around 10 W m−2 over much of the globe. ASR is underestimated by around 30 W m−2 over tropical ocean regions. Away from marine stratocumulus regions, where cloud fraction is underestimated by ERA40, the poor radiation simulation by ERA40 appears to be related to inaccurate radiative properties of cloud rather than inaccurate cloud distributions.

A case study of the radiative forcing of persistent contrails evolving into contrail-induced cirrus

The radiative forcing due to a distinct pattern of persistent contrails that form into contrail-induced cirrus near and over the UK is investigated in detail for a single case study during March 2009. The development of the contrail-induced cirrus is tracked using a number of high-resolution polar orbiting and lower-resolution geostationary satellite instruments and is found to persist for a period of around 18 h, and at its peak, it covers over 50,000 km2. The shortwave (SW) and longwave (LW) radiative forcing of the contrail-induced cirrus is estimated using a combination of geostationary satellite instruments, numerical weather prediction models, and surface observation sites. As expected, the net radiative effect is a relatively small residual of the much stronger but opposing SW and LW effects, locally totaling around 10 W m−2 during daylight hours and 30 W m−2 during nighttime. A simple estimate indicates that this single localized event may have generated a global-mean radiative forcing of around 7% of recent estimates of the persistent contrail radiative forcing due to the entire global aircraft fleet on a diurnally averaged basis. A single aircraft operating in conditions favorable for persistent contrail formation appears to exert a contrail-induced radiative forcing some 5000 times greater (in W m−2 km−1) than recent estimates of the average persistent contrail radiative forcing from the entire civil aviation fleet. This study emphasizes the need to establish whether similar events are common or highly unusual for a confident assessment of the total climate effect of aviation to be made.

Evidence for global circuit current flow through water droplet layers

Abstract Foggy air and clear air have appreciably different electrical conductivities. The conductivity gradient at horizontal droplet boundaries causes droplet charging, as a result of vertical current flow in the global atmospheric electrical circuit. The charging is poorly known, as both the current flow through atmospheric water droplet layers and the air conductivity are poorly characterised experimentally. Surface measurements during three days of continuous fog using new instrument techniques show that a shallow (of order 100 m deep) fog layer still permits the vertical conduction current to pass. Further, the conductivity in the fog is estimated to be approximately 20% lower than in clear air. Assuming a fog transition thickness of one metre, this implies a vertical conductivity gradient of order 10 fS m−2 at the boundary. The actual vertical conductivity gradient at a cloud boundary would probably be greater, due to the presence of larger droplets in clouds compared to fog, and cleaner, more conductive clear air aloft.

A case study of the radiative forcing of persistent contrails evolving into contrail-induced cirrus

The radiative forcing due to a distinct pattern of persistent contrails that form into contrail-induced cirrus near and over the UK is investigated in detail for a single case study during March 2009. The development of the contrail-induced cirrus is tracked using a number of high-resolution polar orbiting and lower-resolution geostationary satellite instruments and is found to persist for a period of around 18 h, and at its peak, it covers over 50,000 km2. The shortwave (SW) and longwave (LW) radiative forcing of the contrail-induced cirrus is estimated using a combination of geostationary satellite instruments, numerical weather prediction models, and surface observation sites. As expected, the net radiative effect is a relatively small residual of the much stronger but opposing SW and LW effects, locally totaling around 10 W m−2 during daylight hours and 30 W m−2 during nighttime. A simple estimate indicates that this single localized event may have generated a global-mean radiative forcing of around 7% of recent estimates of the persistent contrail radiative forcing due to the entire global aircraft fleet on a diurnally averaged basis. A single aircraft operating in conditions favorable for persistent contrail formation appears to exert a contrail-induced radiative forcing some 5000 times greater (in W m−2 km−1) than recent estimates of the average persistent contrail radiative forcing from the entire civil aviation fleet. This study emphasizes the need to establish whether similar events are common or highly unusual for a confident assessment of the total climate effect of aviation to be made.

A glacier inventory for the Buordakh Massif, Cherskiy Range, northeast Siberia, and evidence for recent glacier recession

The Buordakh Massif, in the Cherskiy Range of northeast Siberia, contains mountains over 3000 in and, despite its and climate, numerous glaciers. This paper presents a glacier inventory for the region and documents some 80 glaciers, which range in size from 0.1 to 10.4 km(2) (total glacierized area is ca. 70 km(2)). The inventory is based on mapping derived from Landsat 7 ETM+ satellite imagery from August 2001, augmented with data from field investigations obtained at that time. The glaciers in this region are of the 'firn-less,' cold, continental type, and their mass balance relies heavily on the formation of superimposed ice. The most recent glacier maximum extents have also been delineated, and these are believed to date from the Little Ice Age (ca. A.D. 1550-1850). Glacier areal extent has reduced by some 14.8 km(2) (ca. 17%) since this most. recent maximum. Of the 80 glaciers catalogued, 49 have undergone a measurable retreat from their most recent maximum extent.