5 resultados para Insertion de liens C-H

em Deakin Research Online - Australia


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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 Csp3-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.

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Bis(p-substituted benzoylmethyl)tellurium dibromides, (p-YC6H4COCH2)2TeBr2, (y=H (1a), Me (1b), MeO (1c)) can be prepared
either by direct insertion of elemental Te across CRf-Br bonds (where CRf refers to α-carbon of a functionalized organic moiety) or by the oxidative addition of bromine to (p-YC6H4COCH2)2Te (y = H (2a), Me (2b), MeO (2c)). Bis(p-substituted benzoylmethyl)tellurium dichlorides, (p-YC6H4COCH2)2TeCh (y = H (3a), Me (3b), MeO (3c)), are prepared by the reaction of the bis(p-substituted benzoylmethyl)tellurides 2a--c with S02Cl2, whereas the corresponding diiodides (p-YC6H4COCH2)2Teh (y = H
(4a), Me (4b), MeO (4c)) can be obtained by the metathetical reaction of la--c with KI, or alternatively, by the oxidative addition of
iodine to 2a--c. The reaction of 2a--c with allyl bromide affords the diorganotellurium dibrornides la--c, rather than the expected
triorganotelluronium bromides. Compounds 1-4 were characterized by elemental analyses, IR spectroscopy, 1H, l3C and 125Te
NMR spectroscopy (solution and solid-state) and in case of Ie also by X-ray crystallography. (p-MeOC6H4COCH2)2TeBr2 (1c) provides, a rare example, among organotellurium compounds, of a supramolecular architecture, where C-H-O hydrogen bonds appear to be the non-covalent intermolecular associative force that dominates the crystal packing.

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Bacterial genomes reflect their adaptation strategies through nucleotide usage trends found in their chromosome composition. Bacteria, unlike eukaryotes contain a wide range of genomic G + C. This wide variability may be viewed as a response to environmental adaptation. Two overarching trends are observed across bacterial genomes, the first, correlates genomic G + C to environmental niches and lifestyle, while the other utilizees intra-genomic G + C incongruence to delineate horizontally transferred material. In this review, we focus on the influence of several properties including biochemical, genetic flows, selection biases, and the biochemical-energetic properties shaping genome composition. Outcomes indicate a trend toward high G + C and larger genomes in free-living organisms, as a result of more complex and varied environments (higher chance for horizontal gene transfer). Conversely, nutrient limiting and nutrient poor environments dictate smaller genomes of low GC in attempts to conserve replication expense. Varied processes including translesion repair mechanisms, phage insertion and cytosine degradation has been shown to introduce higher AT in genomic sequences. We conclude the review with an analysis of current bioinformatics tools seeking to elicit compositional variances and highlight the practical implications when using such techniques.

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When the small-pore zeolite natrolite is compressed at ca. 1.5 GPa and heated to ca. 110 °C in the presence of CO2, the unit cell volume of natrolite expands by 6.8% and ca. 12 wt % of CO2 is contained in the expanded elliptical channels. This CO2 insertion into natrolite is found to be reversible upon pressure release.

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This paper presents a wide band RF MEMS capacitive switch. The LC resonant frequency is reduced from mm wave to X band frequencies at down-state by using a meander type membrane, with the frequency band is being increased by adding two short high impedance lines at both ends of coplanar waveguide (CPW). Moreover, this acts as T-match circuit in up-state position and improves the matching. Simulation results demonstrate that the capacitance ratio reduces from 50 to 21.4, S21 and S11 are less than −10dB for the entire frequency band at down-state and up-state. Also, a comprehensive and complete electric model of the switch is proposed and simulation results agree well with the characteristics of the physical structure of the MEMS switch. Vpull-in and Vpull-out of this switch are 8.1V and 0.3V, respectively.