Synthesis and structural characterization of iron complexes with 2,2,2-tris(1-pyrazolyl)ethanol ligands: Application in the peroxidative oxidation of cyclohexane under mild conditions

The reactions of FeCl2 center dot 2H(2)O and 2,2,2-tris(1-pyrazolyl) ethanol HOCH2C(pz)(3) (1) (pz = pyrazolyl) afford [Fe{HOCH2C(pz)(3)}(2)][FeCl4]Cl (2), [Fe{HOCH2C(pz)(3)}(2)](2)[Fe2OCl6](Cl)(2)center dot 4H(2)O (3 center dot 4H(2)O), [Fe{HOCH2C(pz)(3)}(2)] [FeCl{HOCH2C(pz)(3)}(H2O)(2)](2)(Cl)(4) (4) or [Fe{HOCH2C(pz)(3)}(2)]Cl-2 (5), depending on the experimental conditions. Compounds 1-5 were isolated as air-stable crystalline solids and fully characterized, including (1-4) by single-crystal X-ray diffraction analyses. The latter technique revealed strong intermolecular H-bonds involving the OH group of the scorpionate 2 and 3 giving rise to 1D chains which, in 3, are further expanded to a 2D network with intercalated infinite and almost plane chains of H-interacting water molecules. In 4, intermolecular pi center dot center dot center dot pi interactions involving the pyrazolyl rings are relevant. Complexes 2-5 display a high solubility in water (S-25 degrees C ca. 10-12 mg mL(-1)), a favourable feature towards their application as catalysts (or catalyst precursors) for the peroxidative oxidation of cyclo-hexane to cyclohexanol and cyclohexanone, with aqueous H2O2/MeCN, at room temperature (TON values up to ca. 385). (C) 2011 Elsevier B. V. All rights reserved.

Antimicrobial activity of pyrazine and quinoxaline N,N’-dioxide heterocyclic compounds

The nitrogen heterocyclic organic compounds 1,4 dioxide pyrazine and quinoxaline derivatives have been widely studied due to their potential use as synthetic drugs. The thermochemical study of three N,N´-dioxides: 2,3,5-trimethylpyrazine-1,4-dioxide, tetramethylpyrazine-1,4-dioxide and 6-chloro-2,3-dimethilquinoxaline 1,4-dioxide has been recently developed in order to establish relationships among the energetical, structural and reactivity properties [4,5]. Several studies have reported their pharmacological activity, particularly as antimicrobial agents [1,2,3]. It has also been established a relation between energetical and structural properties and biological activity, once these compounds present N – oxide bonds, increasing their oxidative capacity. The present work reports the study of antimicrobial activity for those compounds against the bacteria Geobacillus stearothermophylus, Staphylococcus aureus, Streptococcus agalactiae, Escherichia coli and also against the yeasts Saccharomyces cerevisiae PYCC 4072, Candida albicans PYCC3436T, Candida tropicalis PYCC, Issatchenka Orientalis PYCC. The determination of the minimal inhibitory concentration (MIC), points to an antimicrobial activity and the preliminary results indicate that these compounds may be potential candidates as antimicrobial drugs with clinical, agriculture or food industries applications.

Synthesis, structure and electrochemical behaviour of Na, Mg-II, Mn-II, Cd-II and Ni-II complexes of 3-(2-carboxyphenylhydrazone)pentane-2,4-dione

Mononuclear manganese(II) [Mn(kappa O-HL)(2)(CH3OH)(4)] (4), nickel(II) [Ni(kappa O-2, kappa N-L)(H2O)(3)] (5), cadmium(II) [Cd(kappa O-2-HL)(2)(CH3OH)(3)] (7), tetranuclear zinc(II) [Zn-4(mu-OH)(2)(1 kappa O:2 kappa O-HL)(4)(kappa O-HL)(2)(H2O)(4)] (6) and polynuclear aqua sodium(I) [Na(H2O)(2)(mu-H2O)(2)](n)(HL)(n) (2) and magnesium(II) [Mg(OH)(H2O)(mu-H2O)(2)](n)(-HL)(n) (3) complexes were synthesized using 3-(2-carboxyphenyl-hydrazone)pentane-2,4-dione (H2L, 1) as a ligand precursor. The complexes were characterized by single crystal X-ray diffraction, elemental analysis, IR, H-1 and C-13 NMR (for 2, 3, 6 and 7) spectroscopies. Mono- or dianionic deprotonated derivatives of H2L display different coordination modes and lead to topologies and nuclearities of the complexes depending on metal ions and conditions used for the syntheses. Extensive intermolecular H-bonds form supramolecular arrangements in 1D chains (4 and 6), 1D chains of the organic anion and 2D networks of the metal-aqua aggregates (2 and 3), 2D networks (7) or even 3D frameworks (5). Electrochemical studies, by cyclic voltammetry and controlled potential electrolysis, show ligand centred redox processes as corroborated by theoretical DFT calculations in terms of LUMO and HOMO compositions. (C) 2012 Elsevier Ltd. All rights reserved.

Matemática na educação Pré-Escolar : esquemas todo-partes

O Singapore Math, método utilizado para o ensino da Matemática em Singapura é, segundo as mais prestigiadas avaliações internacionais, um exemplo bem-sucedido da abordagem «concreto-pictórico-abstrato». Um dos inúmeros procedimentos didáticos são os number bonds (esquemas todo-partes), utilizados no ensino de factos fundamentais relativos à primeira dezena: decomposições, adições e subtrações. Neste artigo, analisaremos o que são, quais as vantagens e a forma de utilização destes esquemas desde a educação pré-escolar.

Estudo da influência das condições de armazenamento nas propriedades e composição do biodiesel

O objectivo deste trabalho era a determinação da influência das condições de armazenamento do biodiesel nas suas propriedades e composição. Para isso foi produzido biodiesel a partir de óleo alimentar usado e armazenado em diferentes condições. O biodiesel foi colocado em frascos de vidro e dividido em três grupos diferentes de temperatura. O primeiro foi colocado a uma temperatura de 6ºC (frigorifico) com frascos fechados e expostos ao ar e água. O segundo grupo foi colocado a uma temperatura de 40ºC (banho termostático) com frascos fechados, abertos ao ar e abertos ao ar e água. O terceiro e ultimo grupo foi colocado à temperatura ambiente (18,6

Comunicação para Lares de Infância e Juventude : contributos para uma mudança de paradigma

Dissertação de Mestrado, Ciências da Comunicação, 22 de Maio de 2015, Universidade dos Açores.

Racionalidade de emissão de obrigações subordinadas: Estudo de caso do Banco Comercial do Atlântico (BCA) Cabo Verde

Mestrado em Contabilidade e Gestão de Instituições Financeiras

How patchy can one get and still condense? The role of dissimilar patches in the interactions of colloidal particles

We investigate the influence of strong directional, or bonding, interactions on the phase diagram of complex fluids, and in particular on the liquid-vapour critical point. To this end we revisit a simple model and theory for associating fluids which consist of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the interactions between each pair of spots have strengths [image omitted], [image omitted] and [image omitted]. The theory is applied over the whole range of bonding strengths and results are interpreted in terms of the equilibrium cluster structures of the coexisting phases. In systems where unlike sites do not interact (i.e. where [image omitted]), the critical point exists all the way to [image omitted]. By contrast, when [image omitted], there is no critical point below a certain finite value of [image omitted]. These somewhat surprising results are rationalised in terms of the different network structures of the two systems: two long AA chains are linked by one BB bond (X-junction) in the former case, and by one AB bond (Y-junction) in the latter. The vapour-liquid transition may then be viewed as the condensation of these junctions and we find that X-junctions condense for any attractive [image omitted] (i.e. for any fraction of BB bonds), whereas condensation of the Y-junctions requires that [image omitted] be above a finite threshold (i.e. there must be a finite fraction of AB bonds).

Criticality of colloids with distinct interaction patches: The limits of linear chains, hyperbranched polymers, and dimers

We use a simple model of associating fluids which consists of spherical particles having a hard-core repulsion, complemented by three short-ranged attractive sites on the surface (sticky spots). Two of the spots are of type A and one is of type B; the bonding interactions between each pair of spots have strengths epsilon(AA), epsilon(BB), and epsilon(AB). The theory is applied over the whole range of bonding strengths and the results are interpreted in terms of the equilibrium cluster structures of the phases. In addition to our numerical results, we derive asymptotic expansions for the free energy in the limits for which there is no liquid-vapor critical point: linear chains (epsilon(AA)not equal 0, epsilon(AB)=epsilon(BB)=0), hyperbranched polymers (epsilon(AB)not equal 0, epsilon(AA)=epsilon(BB)=0), and dimers (epsilon(BB)not equal 0, epsilon(AA)=epsilon(AB)=0). These expansions also allow us to calculate the structure of the critical fluid by perturbing around the above limits, yielding three different types of condensation: of linear chains (AA clusters connected by a few AB or BB bonds); of hyperbranched polymers (AB clusters connected by AA bonds); or of dimers (BB clusters connected by AA bonds). Interestingly, there is no critical point when epsilon(AA) vanishes despite the fact that AA bonds alone cannot drive condensation.

Caminha sílaba a sílaba

Eugénio de Andrade (1923-2005) é um dos mais celebrados e traduzidos poetas portugueses contemporâneos, com mais de trinta volumes de poesia, e vários prémios nacionais e internacionais. Como poeta atento e turista curioso, Andrade viajou com frequência para Espanha, França, Itália e Grécia, ao encontro de outros escritores (Vicente Aleixandre, Dámaso Alonso, etc.), e visitou diversas cidades e locais históricos. Recorrentemente, menciona Madrid, Valverde del Fresno, Roma, Delfos, Tebas, Súnion, Veneza, Brindisi, Corfu, etc. Em resultado destas viagens, existem, na sua poesia, poemas em prosa e crónicas, abundantes referências aos países, cultura e paisagem natural do Mediterrâneo. Eugénio de Andrade captura poeticamente o ―genius loci‖, realçando os laços entre os povos, a fauna, a flora e o clima. Desde os primeiros escritos até ao seu último livro, o poeta coerentemente apresenta uma ―visão mediterrânica‖. Recorrendo às suas obras e a excertos de algumas das entrevistas que concedeu, este artigo exemplifica, analisa e avalia estes aspectos, explorando uma faceta menos conhecida da obra eugeniana.

Memória de longo prazo nos retornos acionistas dos índices de referência da euronext, implicações para a hipótese de mercados eficientes e contributo fractal para aperfeiçoamento do capital asset pricing model

Não existe uma definição única de processo de memória de longo prazo. Esse processo é geralmente definido como uma série que possui um correlograma decaindo lentamente ou um espectro infinito de frequência zero. Também se refere que uma série com tal propriedade é caracterizada pela dependência a longo prazo e por não periódicos ciclos longos, ou que essa característica descreve a estrutura de correlação de uma série de longos desfasamentos ou que é convencionalmente expressa em termos do declínio da lei-potência da função auto-covariância. O interesse crescente da investigação internacional no aprofundamento do tema é justificado pela procura de um melhor entendimento da natureza dinâmica das séries temporais dos preços dos ativos financeiros. Em primeiro lugar, a falta de consistência entre os resultados reclama novos estudos e a utilização de várias metodologias complementares. Em segundo lugar, a confirmação de processos de memória longa tem implicações relevantes ao nível da (1) modelação teórica e econométrica (i.e., dos modelos martingale de preços e das regras técnicas de negociação), (2) dos testes estatísticos aos modelos de equilíbrio e avaliação, (3) das decisões ótimas de consumo / poupança e de portefólio e (4) da medição de eficiência e racionalidade. Em terceiro lugar, ainda permanecem questões científicas empíricas sobre a identificação do modelo geral teórico de mercado mais adequado para modelar a difusão das séries. Em quarto lugar, aos reguladores e gestores de risco importa saber se existem mercados persistentes e, por isso, ineficientes, que, portanto, possam produzir retornos anormais. O objetivo do trabalho de investigação da dissertação é duplo. Por um lado, pretende proporcionar conhecimento adicional para o debate da memória de longo prazo, debruçando-se sobre o comportamento das séries diárias de retornos dos principais índices acionistas da EURONEXT. Por outro lado, pretende contribuir para o aperfeiçoamento do capital asset pricing model CAPM, considerando uma medida de risco alternativa capaz de ultrapassar os constrangimentos da hipótese de mercado eficiente EMH na presença de séries financeiras com processos sem incrementos independentes e identicamente distribuídos (i.i.d.). O estudo empírico indica a possibilidade de utilização alternativa das obrigações do tesouro (OT’s) com maturidade de longo prazo no cálculo dos retornos do mercado, dado que o seu comportamento nos mercados de dívida soberana reflete a confiança dos investidores nas condições financeiras dos Estados e mede a forma como avaliam as respetiva economias com base no desempenho da generalidade dos seus ativos. Embora o modelo de difusão de preços definido pelo movimento Browniano geométrico gBm alegue proporcionar um bom ajustamento das séries temporais financeiras, os seus pressupostos de normalidade, estacionariedade e independência das inovações residuais são adulterados pelos dados empíricos analisados. Por isso, na procura de evidências sobre a propriedade de memória longa nos mercados recorre-se à rescaled-range analysis R/S e à detrended fluctuation analysis DFA, sob abordagem do movimento Browniano fracionário fBm, para estimar o expoente Hurst H em relação às séries de dados completas e para calcular o expoente Hurst “local” H t em janelas móveis. Complementarmente, são realizados testes estatísticos de hipóteses através do rescaled-range tests R/S , do modified rescaled-range test M - R/S e do fractional differencing test GPH. Em termos de uma conclusão única a partir de todos os métodos sobre a natureza da dependência para o mercado acionista em geral, os resultados empíricos são inconclusivos. Isso quer dizer que o grau de memória de longo prazo e, assim, qualquer classificação, depende de cada mercado particular. No entanto, os resultados gerais maioritariamente positivos suportam a presença de memória longa, sob a forma de persistência, nos retornos acionistas da Bélgica, Holanda e Portugal. Isto sugere que estes mercados estão mais sujeitos a maior previsibilidade (“efeito José”), mas também a tendências que podem ser inesperadamente interrompidas por descontinuidades (“efeito Noé”), e, por isso, tendem a ser mais arriscados para negociar. Apesar da evidência de dinâmica fractal ter suporte estatístico fraco, em sintonia com a maior parte dos estudos internacionais, refuta a hipótese de passeio aleatório com incrementos i.i.d., que é a base da EMH na sua forma fraca. Atendendo a isso, propõem-se contributos para aperfeiçoamento do CAPM, através da proposta de uma nova fractal capital market line FCML e de uma nova fractal security market line FSML. A nova proposta sugere que o elemento de risco (para o mercado e para um ativo) seja dado pelo expoente H de Hurst para desfasamentos de longo prazo dos retornos acionistas. O expoente H mede o grau de memória de longo prazo nos índices acionistas, quer quando as séries de retornos seguem um processo i.i.d. não correlacionado, descrito pelo gBm(em que H = 0,5 , confirmando- se a EMH e adequando-se o CAPM), quer quando seguem um processo com dependência estatística, descrito pelo fBm(em que H é diferente de 0,5, rejeitando-se a EMH e desadequando-se o CAPM). A vantagem da FCML e da FSML é que a medida de memória de longo prazo, definida por H, é a referência adequada para traduzir o risco em modelos que possam ser aplicados a séries de dados que sigam processos i.i.d. e processos com dependência não linear. Então, estas formulações contemplam a EMH como um caso particular possível.

Automatic learning for the classification of chemical reactions and in statistical thermodynamics

This Thesis describes the application of automatic learning methods for a) the classification of organic and metabolic reactions, and b) the mapping of Potential Energy Surfaces(PES). The classification of reactions was approached with two distinct methodologies: a representation of chemical reactions based on NMR data, and a representation of chemical reactions from the reaction equation based on the physico-chemical and topological features of chemical bonds. NMR-based classification of photochemical and enzymatic reactions. Photochemical and metabolic reactions were classified by Kohonen Self-Organizing Maps (Kohonen SOMs) and Random Forests (RFs) taking as input the difference between the 1H NMR spectra of the products and the reactants. The development of such a representation can be applied in automatic analysis of changes in the 1H NMR spectrum of a mixture and their interpretation in terms of the chemical reactions taking place. Examples of possible applications are the monitoring of reaction processes, evaluation of the stability of chemicals, or even the interpretation of metabonomic data. A Kohonen SOM trained with a data set of metabolic reactions catalysed by transferases was able to correctly classify 75% of an independent test set in terms of the EC number subclass. Random Forests improved the correct predictions to 79%. With photochemical reactions classified into 7 groups, an independent test set was classified with 86-93% accuracy. The data set of photochemical reactions was also used to simulate mixtures with two reactions occurring simultaneously. Kohonen SOMs and Feed-Forward Neural Networks (FFNNs) were trained to classify the reactions occurring in a mixture based on the 1H NMR spectra of the products and reactants. Kohonen SOMs allowed the correct assignment of 53-63% of the mixtures (in a test set). Counter-Propagation Neural Networks (CPNNs) gave origin to similar results. The use of supervised learning techniques allowed an improvement in the results. They were improved to 77% of correct assignments when an ensemble of ten FFNNs were used and to 80% when Random Forests were used. This study was performed with NMR data simulated from the molecular structure by the SPINUS program. In the design of one test set, simulated data was combined with experimental data. The results support the proposal of linking databases of chemical reactions to experimental or simulated NMR data for automatic classification of reactions and mixtures of reactions. Genome-scale classification of enzymatic reactions from their reaction equation. The MOLMAP descriptor relies on a Kohonen SOM that defines types of bonds on the basis of their physico-chemical and topological properties. The MOLMAP descriptor of a molecule represents the types of bonds available in that molecule. The MOLMAP descriptor of a reaction is defined as the difference between the MOLMAPs of the products and the reactants, and numerically encodes the pattern of bonds that are broken, changed, and made during a chemical reaction. The automatic perception of chemical similarities between metabolic reactions is required for a variety of applications ranging from the computer validation of classification systems, genome-scale reconstruction (or comparison) of metabolic pathways, to the classification of enzymatic mechanisms. Catalytic functions of proteins are generally described by the EC numbers that are simultaneously employed as identifiers of reactions, enzymes, and enzyme genes, thus linking metabolic and genomic information. Different methods should be available to automatically compare metabolic reactions and for the automatic assignment of EC numbers to reactions still not officially classified. In this study, the genome-scale data set of enzymatic reactions available in the KEGG database was encoded by the MOLMAP descriptors, and was submitted to Kohonen SOMs to compare the resulting map with the official EC number classification, to explore the possibility of predicting EC numbers from the reaction equation, and to assess the internal consistency of the EC classification at the class level. A general agreement with the EC classification was observed, i.e. a relationship between the similarity of MOLMAPs and the similarity of EC numbers. At the same time, MOLMAPs were able to discriminate between EC sub-subclasses. EC numbers could be assigned at the class, subclass, and sub-subclass levels with accuracies up to 92%, 80%, and 70% for independent test sets. The correspondence between chemical similarity of metabolic reactions and their MOLMAP descriptors was applied to the identification of a number of reactions mapped into the same neuron but belonging to different EC classes, which demonstrated the ability of the MOLMAP/SOM approach to verify the internal consistency of classifications in databases of metabolic reactions. RFs were also used to assign the four levels of the EC hierarchy from the reaction equation. EC numbers were correctly assigned in 95%, 90%, 85% and 86% of the cases (for independent test sets) at the class, subclass, sub-subclass and full EC number level,respectively. Experiments for the classification of reactions from the main reactants and products were performed with RFs - EC numbers were assigned at the class, subclass and sub-subclass level with accuracies of 78%, 74% and 63%, respectively. In the course of the experiments with metabolic reactions we suggested that the MOLMAP / SOM concept could be extended to the representation of other levels of metabolic information such as metabolic pathways. Following the MOLMAP idea, the pattern of neurons activated by the reactions of a metabolic pathway is a representation of the reactions involved in that pathway - a descriptor of the metabolic pathway. This reasoning enabled the comparison of different pathways, the automatic classification of pathways, and a classification of organisms based on their biochemical machinery. The three levels of classification (from bonds to metabolic pathways) allowed to map and perceive chemical similarities between metabolic pathways even for pathways of different types of metabolism and pathways that do not share similarities in terms of EC numbers. Mapping of PES by neural networks (NNs). In a first series of experiments, ensembles of Feed-Forward NNs (EnsFFNNs) and Associative Neural Networks (ASNNs) were trained to reproduce PES represented by the Lennard-Jones (LJ) analytical potential function. The accuracy of the method was assessed by comparing the results of molecular dynamics simulations (thermal, structural, and dynamic properties) obtained from the NNs-PES and from the LJ function. The results indicated that for LJ-type potentials, NNs can be trained to generate accurate PES to be used in molecular simulations. EnsFFNNs and ASNNs gave better results than single FFNNs. A remarkable ability of the NNs models to interpolate between distant curves and accurately reproduce potentials to be used in molecular simulations is shown. The purpose of the first study was to systematically analyse the accuracy of different NNs. Our main motivation, however, is reflected in the next study: the mapping of multidimensional PES by NNs to simulate, by Molecular Dynamics or Monte Carlo, the adsorption and self-assembly of solvated organic molecules on noble-metal electrodes. Indeed, for such complex and heterogeneous systems the development of suitable analytical functions that fit quantum mechanical interaction energies is a non-trivial or even impossible task. The data consisted of energy values, from Density Functional Theory (DFT) calculations, at different distances, for several molecular orientations and three electrode adsorption sites. The results indicate that NNs require a data set large enough to cover well the diversity of possible interaction sites, distances, and orientations. NNs trained with such data sets can perform equally well or even better than analytical functions. Therefore, they can be used in molecular simulations, particularly for the ethanol/Au (111) interface which is the case studied in the present Thesis. Once properly trained, the networks are able to produce, as output, any required number of energy points for accurate interpolations.

Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

Acylated cyanoimido-complexes trans-[Mo(NCN){NCN(O)R}(DPPE)(2)]Cl and their reactons with electrophiles: Chemical, electrochemical and theoretical study

Treatment of a dichloromethane solution of trans-[Mo(NCN){NCNC(O)R}(dppe)(2)]Cl [R = Me (1a), Et (1b)] (dppe = Ph2PCH2CH2PPh2) with HBF4, [Et3O][BF4] or EtC(O)Cl gives trans-[Mo(NCN)Cl-(dppe)(2)]X [X = BF4 (2a) or Cl (2b)] and the corresponding acylcyanamides NCN(R')C(O)Et (R' = H, Et or C(O)Et). X-ray diffraction analysis of 2a (X = BF4) reveals a multiple-bond coordination of the cyanoimide ligand. Compounds 1 convert to the bis(cyanoimide) trans-[Mo(NCN)(2)(dppe)(2)] complex upon reaction with an excess of NaOMe (with formation of the respective ester). In an aprotic medium and at a Pt electrode, compounds 1 (R = Me, Et or Ph) undergo a cathodically induced isomerization. Full quantitative kinetic analysis of the voltammetric behaviour is presented and allows the determination of the first-order rate constants and the equilibrium constant of the trans to cis isomerization reaction. The mechanisms of electrophilic addition (protonation) to complexes 1 and the precursor trans[Mo(NCN)(2)(dppe)(2)], as well as the electronic structures, nature of the coordination bonds and electrochemical behaviour of these species are investigated in detail by theoretical methods which indicate that the most probable sites of the proton attack are the oxygen atom of the acyl group and the terminal nitrogen atom, respectively.

Chimpanzees Share Forbidden Fruit

PLoS ONE - www.plosone.org, V.9, e886