Unsaturated σ-hydrocarbyl transition-metal complexes. Part 3. Crystal and molecular structure of trans-chlorobis(diethylphenylphosphine)(vinyl)platinum(II)

The molecular structure of trans-[PtCl(CHCH2)(PEt2Ph)2] has been determined by X-ray diffraction methods. The crystals are orthorhombic, space group Pbcn, with a= 10.686(2), b= 13.832(4), c= 16.129(4)Å, and Z= 4. The structure has been solved by the heavy-atom method and refined by full-matrix least squares to R 0.044 for 1 420 diffractometric intensity data. The crystals contain discrete molecules in which the platinum co-ordination is square planar. The Pt–Cl bond vector coincides with a crystallographic diad axis about which the atoms of the vinyl group are disordered. Selected bond lengths (Å) are Pt–Cl 2.398(4), Pt–P 2.295(3), and Pt–C 2.03(2). The Pt–CC angle is 127(2)°. From a survey of the available structural data it is concluded that there is little, if any, back donation from platinum to carbon in platinum–alkenyl linkages.

Syntheses and crystal structures of [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], two novel heteroleptic tin(II) compounds derived from [Sn-{2-[(Me3Si)2C]C5H4N}Cl], and for [{Sn(C6H2Pri3-2,4,6)2}3] 3, a structural redetermination

Two novel, monomeric heteroleptic tin(II) derivatives, [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], have been prepared, characterised by multinuclear NMR spectroscopies and their molecular structures determined by single crystal X-ray diffraction. Both compounds were prepared from the corresponding heteroleptic tin(II) chloro-analogue, [Sn{2-[(Me3Si)2C]C5H4N}Cl], and thus demonstrate the utility of this compound as a precursor to further examples of heteroleptic tin(II) derivatives: such compounds are often unstable with respect to ligand redistribution. In each case, the central tin(II) is three-co-ordinate. Crystals of trimeric [{Sn(C6H2Pri3-2,4,6)2}3] 3 were found to undergo a solid state phase transition, which may be ascribed to ordering of the ligand isopropyl groups. At 220 K the unit cell is orthorhombic, space group Pna21, compared with monoclinic, space group P21/c, for the same crystals at 298 K, in which there is an effective tripling of the now b (originally c) axis. This result illustrates the extreme crowding generated by this bulky aryl ligand.

Copper deposition on TiO2 from copper(II)hexafluoroacetylacetonate

The authors have studied the adsorption of CuII(hfac)2 on the surface of a model oxide system, TiO2(110), and probed the molecular stability with respect to thermal cycling, using atomic scale imaging by scanning tunneling microscopy supported by x-ray photoemission spectroscopy. They find that at 473 K, the adsorbed metal-organic molecules begin to dissociate and release Cu atoms which aggregate and form Cu nanoparticles. These Cu nanoparticles ripen over time and the size (height) distribution develops into a bimodal distribution. Unlike other organometallic systems, which show a bimodal distribution due to enhanced nucleation or growth at surface step edges, the nanoparticles do not preferentially form at steps. The reduced mobility of the Cu islands may be related to the co-adsorbed ligands that remain in very small clusters on the surface.

Synthesis and properties of new Mo(II) complexes with N-heterocyclic and ferrocenyl ligands

New Mo(II) complexes with 2,2'-dipyridylamine (L1), [Mo(CH(3)CN)(eta(3)-C(3)H(5))(CO)(2)(L1)]OTf (C1a) and [{MoBr(eta(3)-C(3)H(5))(CO)(2)(L1)}(2)(4,4'-bipy)](PF(6))(2) (C1b), with {[bis(2-pyridyl)amino]carbonyl}ferrocene (L2), [MoBr(eta(3)-C(3)H(5))(CO)(2)(L2)] (C2), and with the new ligand N,N-bis(ferrocenecarbonyl)-2-aminopyridine (L3), [MoBr(eta(3)-C(3)H(5))(CO)(2)(L3)] (C3), were prepared and characterized by FTIR and (1)H and (13)C NMR spectroscopy. C1a, C1b, L3, and C2 were also structurally characterized by single crystal X-ray diffraction. The Mo(II) coordination sphere in all complexes features the facial arrangement of allyl and carbonyl ligands, with the axial isomer present in C1a and C2, and the equatorial in the binuclear C1b. In both C1a and C1b complexes, the L1 ligand is bonded to Mo(II) through the nitrogen atoms and the NH group is involved in hydrogen bonds. The X-ray single crystal structure of C2 shows that L2 is coordinated in a kappa(2)-N,N-bidentate chelating fashion. Complex C3 was characterized as [MoBr(eta(3)-C(3)H(5))(CO)(2)(L3)] with L3 acting as a kappa(2)-N,O-bidentate ligand, based on the spectroscopic data, complemented by DFT calculations. The electrochemical behavior of the monoferrocenyl and diferrocenyl ligands L2 and L3 has been studied together with that of their Mo(II) complexes C2 and C3. As much as possible, the nature of the different redox changes has been confirmed by spectrophotometric measurements. The nature of the frontier orbitals, namely the localization of the HOMO in Mo for both in C2 and C3, was determined by DFT studies.

Structural and magnetic studies of Schiff base complexes of nickel(ii) nitrite: change in crystalline state, ligand rearrangement and a very rare μ-nitrito-1κO:2κN:3κO′ bridging mode

Four new nickel(II) complexes, [Ni2L2(NO2)2]·CH2Cl2·C2H5OH, 2H2O (1), [Ni2L2(DMF)2(m-NO2)]ClO4·DMF (2a), [Ni2L2(DMF)2(m-NO2)]ClO4 (2b) and [Ni3L¢2(m3-NO2)2(CH2Cl2)]n·1.5H2O (3) where HL = 2-[(3-amino-propylimino)-methyl]-phenol, H2L¢ = 2-({3-[(2-hydroxy-benzylidene)-amino]-propylimino}-methyl)-phenol and DMF = N,N-dimethylformamide, have been synthesized starting with the precursor complex [NiL2]·2H2O, nickel(II) perchlorate and sodium nitrite and characterized structurally and magnetically. The structural analyses reveal that in all the complexes, NiII ions possess a distorted octahedral geometry. Complex 1 is a dinuclear di-m2-phenoxo bridged species in which nitrite ion acts as chelating co-ligand. Complexes 2a and 2b also consist of dinuclear entities, but in these two compounds a cis-(m-nitrito-1kO:2kN) bridge is present in addition to the di-m2-phenoxo bridge. The molecular structures of 2a and 2b are equivalent; they differ only in that 2a contains an additional solvated DMF molecule. Complex 3 is formed by ligand rearrangement and is a one-dimensional polymer in which double phenoxo as well as m-nitrito-1kO:2kN bridged trinuclear units are linked through a very rare m3-nitrito-1kO:2kN:3kO¢ bridge. Analysis of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the nickel(II) ions in four complexes, with exchange parameters J of -5.26, -11.45, -10.66 and -5.99 cm-1 for 1, 2a, 2b and 3, respectively

An effective approach for land-cover classification from airborne lidar fused with co-registered data

Airborne lidar provides accurate height information of objects on the earth and has been recognized as a reliable and accurate surveying tool in many applications. In particular, lidar data offer vital and significant features for urban land-cover classification, which is an important task in urban land-use studies. In this article, we present an effective approach in which lidar data fused with its co-registered images (i.e. aerial colour images containing red, green and blue (RGB) bands and near-infrared (NIR) images) and other derived features are used effectively for accurate urban land-cover classification. The proposed approach begins with an initial classification performed by the Dempster–Shafer theory of evidence with a specifically designed basic probability assignment function. It outputs two results, i.e. the initial classification and pseudo-training samples, which are selected automatically according to the combined probability masses. Second, a support vector machine (SVM)-based probability estimator is adopted to compute the class conditional probability (CCP) for each pixel from the pseudo-training samples. Finally, a Markov random field (MRF) model is established to combine spatial contextual information into the classification. In this stage, the initial classification result and the CCP are exploited. An efficient belief propagation (EBP) algorithm is developed to search for the global minimum-energy solution for the maximum a posteriori (MAP)-MRF framework in which three techniques are developed to speed up the standard belief propagation (BP) algorithm. Lidar and its co-registered data acquired by Toposys Falcon II are used in performance tests. The experimental results prove that fusing the height data and optical images is particularly suited for urban land-cover classification. There is no training sample needed in the proposed approach, and the computational cost is relatively low. An average classification accuracy of 93.63% is achieved.

A closer look at chaotic advection in the stratosphere: part II: statistical diagnostics

Statistical diagnostics of mixing and transport are computed for a numerical model of forced shallow-water flow on the sphere and a middle-atmosphere general circulation model. In particular, particle dispersion statistics, transport fluxes, Liapunov exponents (probability density functions and ensemble averages), and tracer concentration statistics are considered. It is shown that the behavior of the diagnostics is in accord with that of kinematic chaotic advection models so long as stochasticity is sufficiently weak. Comparisons with random-strain theory are made.

Nonlinear saturation of baroclinic instability: part II: continuously stratified fluid

Rigorous upper bounds are derived that limit the finite-amplitude growth of arbitrary nonzonal disturbances to an unstable baroclinic zonal flow in a continuously stratified, quasi-geostrophic, semi-infinite fluid. Bounds are obtained bath on the depth-integrated eddy potential enstrophy and on the eddy available potential energy (APE) at the ground. The method used to derive the bounds is essentially analogous to that used in Part I of this study for the two-layer model: it relies on the existence of a nonlinear Liapunov (normed) stability theorem, which is a finite-amplitude generalization of the Charney-Stern theorem. As in Part I, the bounds are valid both for conservative (unforced, inviscid) flow, as well as for forced-dissipative flow when the dissipation is proportional to the potential vorticity in the interior, and to the potential temperature at the ground. The character of the results depends on the dimensionless external parameter γ = f02ξ/β0N2H, where ξ is the maximum vertical shear of the zonal wind, H is the density scale height, and the other symbols have their usual meaning. When γ ≫ 1, corresponding to “deep” unstable modes (vertical scale ≈H), the bound on the eddy potential enstrophy is just the total potential enstrophy in the system; but when γ≪1, corresponding to ‘shallow’ unstable modes (vertical scale ≈γH), the eddy potential enstrophy can be bounded well below the total amount available in the system. In neither case can the bound on the eddy APE prevent a complete neutralization of the surface temperature gradient which is in accord with numerical experience. For the special case of the Charney model of baroclinic instability, and in the limit of infinitesimal initial eddy disturbance amplitude, the bound states that the dimensionless eddy potential enstrophy cannot exceed (γ + 1)2/24&gamma2h when γ ≥ 1, or 1/6;&gammah when γ ≤ 1; here h = HN/f0L is the dimensionless scale height and L is the width of the channel. These bounds are very similar to (though of course generally larger than) ad hoc estimates based on baroclinic-adjustment arguments. The possibility of using these kinds of bounds for eddy-amplitude closure in a transient-eddy parameterization scheme is also discussed.

Motion of the dayside polar cap boundary during substorm cycles: II. Generation of poleward-moving events and polar cap patches by pulses in the magnetopause reconnection rate

Using data from the EISCAT (European Incoherent Scatter) VHF and CUTLASS (Co-operative UK Twin- Located Auroral Sounding System) HF radars, we study the formation of ionospheric polar cap patches and their relationship to the magnetopause reconnection pulses identified in the companion paper by Lockwood et al. (2005). It is shown that the poleward-moving, high-concentration plasma patches observed in the ionosphere by EISCAT on 23 November 1999, as reported by Davies et al. (2002), were often associated with corresponding reconnection rate pulses. However, not all such pulses generated a patch and only within a limited MLT range (11:00–12:00 MLT) did a patch result from a reconnection pulse. Three proposed mechanisms for the production of patches, and of the concentration minima that separate them, are analysed and evaluated: (1) concentration enhancement within the patches by cusp/cleft precipitation; (2) plasma depletion in the minima between the patches by fast plasma flows; and (3) intermittent injection of photoionisation-enhanced plasma into the polar cap. We devise a test to distinguish between the effects of these mechanisms. Some of the events repeat too frequently to apply the test. Others have sufficiently long repeat periods and mechanism (3) is shown to be the only explanation of three of the longer-lived patches seen on this day. However, effect (2) also appears to contribute to some events. We conclude that plasma concentration gradients on the edges of the larger patches arise mainly from local time variations in the subauroral plasma, via the mechanism proposed by Lockwood et al. (2000).

Revisiting cangitoxin, a sea anemone peptide: Purification and characterization of cangitoxins II and III from the venom of Bunodosoma cangicum

Sodium channel toxins from sea anemones are employed as tools for dissecting the biophysical properties of inactivation in voltage-gated sodium channels. Cangitoxin (CGTX) is a peptide containing 48 amino acid residues and was formerly purified from Bunodosoma cangicum. Nevertheless, previous works reporting, the isolation procedures for such peptide from B. cangicum secretions are controversial and may lead to incorrect information. In this paper, we report a simple and rapid procedure, consisting of two chromatographic steps, in order to obtain a CGTX analog directly from sea anemone venom. We also report a substitution of N16D in this peptide sample and the co-elution of an inseparable minor isoform presenting the R14H substitution. Peptides are named as CGTX-II and CGTX-III, and their effects over Nav1.1 channels in patch clamp experiments are demonstrated. (c) 2008 Elsevier Ltd. All rights reserved.

Nop53p interacts with 5.8S rRNA co-transcriptionally, and regulates processing of pre-rRNA by the exosome

In eukaryotes, pre-rRNA processing depends on a large number of nonribosomal trans-acting factors that form intriguingly organized complexes. One of the early stages of pre-rRNA processing includes formation of the two intermediate complexes pre-40S and pre-60S, which then form the mature ribosome subunits. Each of these complexes contains specific pre-rRNAs, ribosomal proteins and processing factors. The yeast nucleolar protein Nop53p has previously been identified in the pre-60S complex and shown to affect pre-rRNA processing by directly binding to 5.8S rRNA, and to interact with Nop17p and Nip7p, which are also involved in this process. Here we show that Nop53p binds 5.8S rRNA co-transcriptionally through its N-terminal region, and that this protein portion can also partially complement growth of the conditional mutant strain Delta nop53/GAL:NOP53. Nop53p interacts with Rrp6p and activates the exosome in vitro. These results indicate that Nop53p may recruit the exosome to 7S pre-rRNA for processing. Consistent with this observation and similar to the observed in exosome mutants, depletion of Nop53p leads to accumulation of polyadenylated pre-rRNAs.

The mer-[RuCl(3)(dppb)(H(2)O)] complex: A versatile tool for synthesis of Ru(II) compounds

The complex mer-[RuCl(3)(dppb)(H(2)O)] [dppb = 1,4-bis(diphenylphosphino)butane] was used as a precursor in the synthesis of the complexes tc-[RuCl(2)(CO)(2)(dppb)], ct-[RuCl(2)(CO)(2)(dppb)]. cis-[RuCl(2)(dppb)(Cl-bipy)], [RuCl(2Ac4mT)(dppb)] (2Ac4mT = N(4)-meta-tolyl-2-acetylpyridine thiosemicarbazone ion) and trans-[RuCl(2)(dppb)(mang)] (mang = mangiferin or 1,3,6,7-tetrahydroxyxanthone-C2-beta-D-glucoside) complexes. For the synthesis of Run complexes, the Ru(III) atom in mer-[RuCl(3)(dppb)(H(2)O)] may be reduced by H(2)(g), forming the intermediate [Ru(2)Cl(4)(dppb)(2)], or by a ligand (such as H2Ac4mT or mangiferin). The X-ray structures of the cis-[RuCl(2)(dppb)(Cl-bipy)], tc-[RuCl(2)(CO)(2)(dppb)] and [RuCl(2Ac4mT)(dPpb)] complexes were determined. (C) 2010 Elsevier Ltd. All rights reserved.

On the synthesis and structures of the complexes [RuCl(L)(dppb)(N-N)]PF(6) (L = CO, py or 4-NH(2)py; dppb=1,4-bis(diphenylphosphino)butane; N-N=2,2 `-bipyridine or 1,10-phenanthroline) and [(dppb)(CO)Cl(2)-Ru-pz-RuCl(2)(CO)(dppb)] (pz = pyrazine)

The ""Ru(P-P)"" unit (P-P = diphosphine) is recognized to be an important core in catalytic species for hydrogenation of unsaturated organic substrates. Thus, in this study we synthesized six new complexes containing this core, including the binuclear complex [(dppb)(CO)Cl(2)Ru-pz-RuCl(2)(CO)(dPPb)] (pz = pyrazine) which can be used as a precursor for the synthesis of cationic carbonyl species of general formula [RuCl(CO)(dppb)(N-N)]PF(6) (N-N = diimine). Complexes with the formula (RuCl(py)(dppb)(N-N)]PF(6) were synthesized by exhaustive electrolysis of these carbonyl compounds or from the precursors [RuCl(2)(dppb)(N-N)]. The new complexes were characterized by microanalysis, conductivity measurements, IR and (31)P{(1)H)} NMR spectroscopy, cyclic voltammetry and X-ray crystallography. (C) 2010 Elsevier Ltd. All rights reserved.