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showing 10 items of 36149 documents
Co–Co and Co–Fe cyano-bridged pentanuclear clusters based on a methylpyrazinyl-diamine tetradentate ligand: spin crossover and metal substitution eff…
2017
A pentanuclear [CoII3CoIII2] cluster complex has been developed by a solvothermal synthesis. Its highly stable metal-mixed Fe–Co derivatives display robust spin crossover (T1/2 = 268 K) controlled by the degree of substitution.
Amino‐Substituted Ferra‐bis(tricarbollides) − Metallatricarbaboranes Designed for Linear Molecular Constructions
2004
Reactions between high purity FeCl2 and the anion [nido-7-(tBuHN)-7,8,9-C3B8H10)]− (1−) have been used for efficient syntheses of the twelve-vertex double-cluster metallatricarbollide complexes of the para,para (p,p) type [closo-9,9′(RHN)2-commo-2,2′-FeII-1,7,9-(C3B8H10)-1′,7′,9′-(C3B8H10)] (2) (2a, R = tBu and 2b, R = H) (yields 42−45% for 2a). Compound 2b, which contains two reactive amino substituents conveniently attached to the tricarbollide subclusters in p-positions with respect to the metal center, was prepared via facile cleavage of the tBu substituent in 2a either by AlCl3 or by thermal means. The structure of 2b constitutes a good setting for the synthesis of building blocks for …
Solution, structural and photophysical aspects of substituent effects in the N^N ligand in [Ir(C^N)2(N^N)]+ complexes
2013
The syntheses and properties of a series of eleven new [Ir(ppy)2(N^N)][PF6] complexes (Hppy = 2-phenylpyridine) are reported. The N^N ligands are based on 2,2-bipyridine (bpy), substituted in the 6- or 5-positions with groups that are structurally and electronically diverse. All but two of the N^N ligands incorporate an aromatic ring, designed to facilitate intra-cation face-to-face π-interactions between the N^N and one [ppy](-) ligand. Within the set of ligands, 6-(3-tolyl)-2,2'-bipyridine (5), 4,6-bis(4-nitrophenyl)-2,2'-bipyridine (9), and 4,6-bis(3,4,5-trimethoxyphenyl)-2,2'-bipyridine (10) are new and their characterization includes single crystal structures of 9, and two polymorphs o…
Catalytic Asymmetric Reactions Involving the Seven-Membered Cyclic Imine Moieties Present in Dibenzo[b,f][1,4]oxazepines
2017
The dibenzo[b,f][1,4]oxazepine scaffold is a privileged structure in medicinal chemistry that displays a wide variety of biological and pharmacological activities. However, catalytic asymmetric methodologies for the synthesis of chiral dibenzo[b,f][1,4]oxazepine derivatives are scarce in the literature. This microreview presents an overview of enantioselective reactions in which these cyclic seven-membered imines are used as electrophiles, including their substrate scope, limitations and application to the synthesis of related compounds.
Substituent effect on the σ- and π-electron structure of the nitro group and the ring in meta- and para-substituted nitrobenzenes
2017
An application of quantum chemical modeling allowed us to investigate a substituent effect on a σ and π electron structure of a ring and the nitro group in a series of meta- and para-X-substituted nitrobenzene derivatives (X = NMe2, NHMe, NH2, OH, OMe, Me, H, F, Cl, CF3, CN, CHO, COMe, CONH2, COOH, NO2, and NO). The obtained pEDA and sEDA parameters (the π- and σ-electron structure characteristics of a given planar fragment of the system obtained by the summation of π- and σ-orbital occupancies, respectively) of the NO2 group and the benzene ring allowed us to reveal the impact of the substituents on their mutual relations as well as to analyze them from the viewpoint of substituent charact…
Carbon monoxide activation by a molecular aluminium imide: C-O bond cleavage and C-C bond formation
2020
Anionic molecular imide complexes of aluminium are accessible via a rational synthetic approach involving the reactions of organo azides with a potassium aluminyl reagent. In the case of K2 [(NON)Al(NDipp)]2 (NON=4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene; Dipp=2,6-diisopropylphenyl) structural characterization by X-ray crystallography reveals a short Al-N distance, which is thought primarily to be due to the low coordinate nature of the nitrogen centre. The Al-N unit is highly polar, and capable of the activation of relatively inert chemical bonds, such as those found in dihydrogen and carbon monoxide. In the case of CO, uptake of two molecules of the substrate…
Electrochemical and spectroelectrochemical studies of β-phosphorylated Zn porphyrins
2013
The electrochemical and spectroelectrochemical properties of two β-phosphorylated Zn porphyrins, [2-diethoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (1) and [2-diisopropoxyphosphoryl-5,10,15,20-tetraphenylporphyrinato]zinc (2), are reported in CH 2 Cl 2 and PhCN containing tetrabutylammonium perchlorate (TBAP) or tetrabutylammonium hexafluorophosphate (TBAPF6) as supporting electrolyte. Under certain solution conditions, three one-electron reductions are observed, with the last process being attributed to the product of a chemical reaction following formation of the porphyrin dianion. Two or three oxidations are observed for the same compounds, again depending upon the solution c…
Transnational bodies: Embodiment of transnational settings
2016
AbstractThe everyday life of more and more people is characterized by transnationalism. People increasingly interact across borders and in a network of transnational relationships. While interactions may be border-crossing, the actors’ body remains situated and limited in time and space. However, the thesis of this paper is that transnationalism processes are embodied. Thus, we speak of an embodiment of transnational settings. We focus on symbolic interactionism – Charles H. Cooley and George H. Mead in particular provide a large repertoire of concepts – to theoretically conceive transnational bodies. To show how transnational embodiment can manifest itself we use the example of young peopl…
Surface sediment dynamics along the shore of Hammamet Gulf (Tunisia, southern Mediterranean)
2016
International audience; In the summer of 2015 the authors analysed grain size and surface sediment composition through high spatial resolution from samples taken at 53 stations along the Hammamet coast (southern Mediterranean Sea). The Acoustic Doppler Current Profiler deployed in this study showed that the surface current flows toward the north-east, parallel to the coast at a maximum speed along the main axis of about 5.9 cm s−1. Near the bottom the current flows toward the north-west at a maximum speed of 2.2 cm s−1. The tide plays a relatively small role in water circulation in Hammamet Gulf. Spatial distribution of particle size, along with speed and current direction analysis, furnish…
Budyko’s Based Method for Annual Runoff Characterization across Different Climatic Areas: an Application to United States
2018
Runoff data knowledge is of fundamental importance for a wide range of hydrological, ecological, and socioeconomic applications. The reconstruction of annual runoff is a fundamental task for several activities related to water resources management, especially for ungauged basins. At catchment scales, the Budyko's framework provides an extremely useful and, in some cases, accurate estimation of the long-term partitioning of precipitation into evapotranspiration and runoff as a function of the prevailing climatic conditions. Recently the same long-term partitioning rules have been successfully used to describe water partitioning also at the annual scale and calculate the annual runoff distrib…