Electronic properties of 4,4 ',5,5 '-tetramethyl-2,2 '-biphosphinine (tmbp) in the redox series fac-[Mn(Br)(CO)(3)(tmbp)], [Mn(CO)(3)(tmbp)](2), and [Mn(CO)(3)(tmbp)](-): crystallographic, spectroelectrochemical, and DFT computational study

Stepwise electrochemical reduction of the complex fac-[Mn(Br)(CO)(3)(tmbp)] (tmbp = 4,4',5,5'-tetramethyl-2,2'-biphosphinine) produces the dimer [Mn(CO)(3)(tmbp)](2) and the five-coordinate anion [Mn(CO)(3)(tmbp)](-). All three members of the redox series have been characterized by single-crystal X-ray diffraction. The crystallographic data provide valuable insight into the localization of the added electrons on the (carbonyl)manganese and tmbp centers. In particular, the formulation of the two-electron-reduced anion as [Mn-0(CO)(3)(tmbp(-))](-) also agrees with the analysis of its IR nu(CO) wavenumbers and with the results of density functional theoretical (DFT) MO calculations on this compound. The strongly delocalized pi-bonding in the anion stabilizes its five-coordinate geometry and results in the appearance of several mixed Mn-to-tmbp charge-transfer/IL(tmbp) transitions in the near-UV-vis spectral region. A thorough voltammetric and UV-vis/IR spectroelectrochemical study of the reduction path provided evidence for a direct formation of [Mn(CO)(3)(tmbp)](-) via a two-electron ECE mechanism involving the [Mn(CO)(3)(tmbp)](.) radical transient. At ambient temperature [Mn(CO)(3)(tmbp)](-) reacts rapidly with nonreduced fac-[Mn(Br)(CO)(3)(tmbp)] to produce [Mn(CO)(3)(tmbp)](2). Comparison with the analogous 2,2'-bipyridine complexes has revealed striking similarity in the bonding properties and reactivity, despite the stronger pi-acceptor character of the tmbp ligand.

Synthesis and structural characterisation of [Pd2(μ-Br)2(PBut3)2], an example of a palladium(I)-palladium(I) dimer

The syntheses, spectroscopic characterisation and in one case (X = Br) the single-crystal structure of the novel PdI–PdI dimers [Pd2(µ-X)2(PBut3)2](X = Br or I) have been determined; preliminary results on their reactions with CO, H2, CNC6H3Me2 and C2H2 have also been obtained.

Can the Deforestation Breeze Change the Rainfall in Amazonia? A Case Study for the BR-163 Highway Region

The authors simulated the effects of Amazonian mesoscale deforestation in the boundary layer and in rainfall with the Brazilian Regional Atmospheric Modeling System (BRAMS) model. They found that both the area and shape (with respect to wind incidence) of deforestation and the soil moisture status contributed to the state of the atmosphere during the time scale of several weeks, with distinguishable patterns of temperature, humidity, and rainfall. Deforestation resulted in the development of a three-dimensional thermal cell, the so-called deforestation breeze, slightly shifted downwind to large-scale circulation. The boundary layer was warmer and drier above 1000-m height and was slightly wetter up to 2000-m height. Soil wetness affected the circulation energetics proportionally to the soil dryness (for soil wetness below similar to 0.6). The shape of the deforestation controlled the impact on rainfall. The horizontal strips lined up with the prevailing wind showed a dominant increase in rainfall, significant up to about 60 000 km(2). On the other hand, in the patches aligned in the opposite direction (north-south), there was both increase and decrease in precipitation in two distinct regions, as a result of clearly separated upward and downward branches, which caused the precipitation to increase for patches up to 15 000 km(2). The authors` estimates for the size of deforestation impacting the rainfall contributed to fill up the low spatial resolution in other previous studies.

Heterobimetallic compounds [Ru(eta(5)-Cp)(dppf)X] (X = Cl, Br, I and N(3)): synthesis, electrochemical analysis, and the crystal structure of [Ru(eta(5)-Cp)(dppf)I] [dppf=1,1`-bis(diphenylphosphino)ferrocene]

A series of new ruthenium-iron based derivatives [Ru(eta(5)-Cp)(dppf)Cl] (1), [Ru(eta(5)-Cp)(dppf)Br] (2), [Ru(eta(5)-Cp)(dppf)I] (3) and [Ru(eta(5)-Cp)(dppf)N(3)] (4) were obtained by reactions of [Ru(eta(5)-Cp)(PPh(3))(2)Cl] with 1,1`-bis(diphenylphosphino) ferrocene (dppf) and characterized by IR, NMR ((1)H, (13)C and (31)P), (57)Fe Mossbauer spectroscopy and cyclic voltammetry. Additionally, the compound (3) was structurally characterized by X-ray crystallography, and the results were as follows: orthorhombic, Pbca, a = 18.2458(10), b = 20.9192(11), c = 34.4138(19) a""<<, alpha = beta = gamma = 90A degrees, V = 13135.3(12) a""<<(3) and Z = 16.

Spin contamination in XOO radicals X = F, Cl, Br, HO: How is the investigation of the HOOO radical affected

We have analysed the effect of spin contamination in the wavefunction of HOOO. At least, two solutions can be found for the HF wavefunction. One, lower in energy, presents a high spin contamination and gives qualitatively incorrect structural parameters. On the other hand, the less contaminated HF reference gives structural parameters that are in better agreement with experiment, and positive spin densities on all atoms. Some of the problems described during previous investigations of HOOO can now be traced to problems in the HF reference. For the first time we report a CCSD(T) estimation of the structure of HOOO cis employing a HF reference with small spin contamination. (C) 2008 Elsevier B.V. All rights reserved.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

Elevers uppfattningar av vad man bör uppnå efter avslutad kurs i Idrott och Hälsa A : En studie av två gymnasieskolor i årskurs 2 – ett elevperspektiv

The purpose of this work is to see if the students, on two separate high schools, understand what skills you should achieve after completing the course in physical education and health A 100 points. The entire study is based on a student perspective. In order to best answer the purpose, the questionnaire used in the "available groups" in schools. The questions for the work are: To what extent and how students perceive what they should achieve after completing the course in Sport and Health A?, Which is the goal, based on the curriculum in Physical Education, that students feel are important to achieve? and how do a comparison like between these two schools on the basis of what students perceive that they must achieve in Sport and Health A?The result shows that the main goal that finds support in the course objectives is an assertion; Has knowledge of what to eat to maintain or improve health, which over 90% of students had checked in. The least important goal was the claim 14; Know woods and fields and carry out outdoor activities, as 30% of students had checked in. The most important goal that does not find support in the course objectives is claim 10; to be reversed to the lessons, which was 88% in response rate among students. Here was the least important goal, claim 6; to be skilled in various ball games, which received 17% of student responses. The findings revealed that there is a clear health perspective in physical education in the studied groups at the two schools, one can also see that there is an uneven distribution of the elements included in the curriculum of Sport and Health A, and the outdoor life and dance is rare in the teaching of the groups studied at the two schools. Finally, it appeared that the lesson content and teaching are likely to have a significant role in student perceptions of course goals.

Processmetoden attraktivt arbete skapar förutsättningar för kollektivt lärande : Organisationer främjar - individen bär ansvaret

Dagens organisationer står inför stora utmaningar i att vara konkurrenskraftiga gentemot omvärlden. De mänskliga resurserna är organisationernas viktigaste faktor för att över huvud taget överleva. För att verksamheten ska kunna förvalta och nyttja medarbetarnas kompetens på rätt sätt behöver det skapas förutsättningar och tillfällen där relationer kan uppstå. Detta är något som diskuteras i både forskning och litteratur så även hur organisationer ska vara uppbyggda för att främja arbetet kring medarbetarna. Denna studie är ett bidrag att använda i organisationer för att arbeta med att utveckla medarbetarnas kollektiva lärande om varandra för att förstärka relationiken. Processmetoden som har använts för att skapa kollektivt lärande hos medarbetarna är Attraktivt arbete. Deltagarna har fått utföra metoden och observationer har gjorts på hur deltagarna har agerat under processen. Resultatet visar att för att åstadkomma ett kollektivt lärande behöver deltagarna visa på engagemang och viljan att lära sig om varandra. Genom dialog skapas förutsättningar att förstå varandra. Det är när förståelsen finns om varandra som relationerna stärks och på så vis skapas relationik.

Room-temperature insertion of elemental tellurium into the Cspł-Br and -I bonds of α-bromo-and α-iodopinacolone

Pinacolyltellurium(IV) dihalides, (t-BuCOCH₂)₂TeX₂ (X ) Br (1b), I (1c)) and Ar(t-BuCOCH₂)TeCl₂ (Ar == 1-C₁₀H₇ (Np) (2a), 2,4,6-Me₃C₆H₂ (Mes) (3a)), are readily prepared at room temperature by the oxidative insertion of elemental tellurium into the C_sp³-Br or -I bond of the α-halopinacolone and by the reaction of ArTeCl₃ with the pinacolone t-BuCOCH₃. The bromides Np(t-BuCOCH₂)TeBr₂ (2b) and Mes(t-BuCOCH₂)TeBr₂ (3b) can be prepared by the addition of bromine to the telluride Ar(t-BuCOCH₂)-Te or of α-bromopinacolone to ArTeBr. Variable-temperature ¹H and ¹³C NMR of the separate signals for the o-Me groups in 3a,b indicate a very high barrier to rotation about the Te-C(aryl) bond. Crystal diffraction data for 1c, 2a-c, and 3b show that intramolecular 1,4-Te …O(C) secondary bonding interactions (SBIs) are retained even in the presence of bulky aryl groups and intermolecular Te …X SBIs are subject to electronic population and steric congestion around the Te(IV) center in the solid state.<br />

Observation of Te···π and X···X Bonding in para-Substituted Diphenyltellurium Dihalides, (p-Me2NC6H4)(p-YC6H4)TeX2(X=Cl, Br, I; Y=H, EtO, Me2N)-

The supramolecular association of the previously described para-dimethylaminophenyl-substituted diorganotellurium dihalides (p-Me₂NC₆H₄)₂TeX₂ (X = Cl (1), Br (2), I (3)) and (p-Me₂NC₆H₄)RTeCl₂ (R = Ph (4), p-EtOC₆H₄ (5)), was investigated by X-ray crystallography. Unlike almost all other structurally characterized diorganotellurium dihalides, (p-Me₂NC₆H₄)₂TeX₂ (X = Cl (1), Br (2), I (3)) reveal no secondary Te∙∙∙X interactions, but X∙∙∙X interactions. The structure of (p-Me₂NC₆H₄)PhTeCl₂ (4) resembles that of Ph₂TeCl₂ and shows one secondary Te∙∙∙Cl contact, whereas (p-Me₂NC₆H₄)(p-EtOC₆H₄)TeCl₂ (5) exhibits neither secondary Te∙∙∙Cl nor Cl∙∙∙Cl interactions. The unusual structural characteristics of 1–5 are attributed to the occurrence of intermolecular Te∙∙∙π and π∙∙∙π contacts associated with quinoid π-electron delocalization across the para-dimethylaminophenyl (1–5) and para-ethoxyphenyl (5) groups.<br /><br /><br />

Análise de comportamento da camada reciclada com espuma de asfalto na rodovia BR-290/RS

A reciclagem com espuma de asfalto realizada na Rodovia BR-290/RS no ano de 2001, entre os km 97 e km 112, pista sentido Porto Alegre, também chamada Pista Sul, foi objeto de estudo nesta dissertação. Este estudo apresenta todas as etapas da reciclagem, desde a elaboração do projeto, as suas considerações, tais como volume de tráfego, clima da região, características funcionais e estruturais do pavimento, execução da camada reciclada, mencionando método de execução e controles adotados e por fim e como foco principal a análise do comportamento da mistura reciclada, compilando dados à época da execução, seis meses e um ano após a execução. Foram aproveitados dois levantamentos deflectométricos um realizado com o FWD(Falling Weight Deflectometer) no mês de dezembro de 2001 e outro realizado no mês de junho de 2002 com a viga eletrônica, também chamada deflectógrafo digital. Através destes levantamentos estimavam-se por retroanálise das bacias de deflexão, utilizando o programa computacional LAYMOD4, os módulos de cada camada do pavimento. Os resultados da reciclagem são satisfatórios. Analisando a camada reciclada isoladamente, comprovam-se várias citações de pesquisadores sobre o tema, tais como: a melhoria das propriedades mecânicas da reciclagem após tempo de cura e a dependência da mistura ao estado de tensões para seu comportamento elástico. Uma avaliação de desempenho foi desenvolvida, com o auxílio do programa PAVESYS9, revelando que o pavimento apresentou boa performance, comprovando mais uma vez, a melhoria no comportamento da camada reciclada com passado tempo de cura, aumentando o módulo de resiliencia e contribuindo menos para o afundamento de trilha de roda.