812 research outputs found

    Understanding the subtleties of frustrated Lewis pair activation of carbonyl compounds by N-Heterocyclic carbene/alkyl gallium pairings

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    This study reports the use of the trisalkylgallium GaR3 (R=CH2 SiMe3 ), containing sterically demanding monosilyl groups, as an effective Lewis-acid component for frustrated Lewis pair activation of carbonyl compounds, when combined with the bulky N-heterocyclic carbene 1,3-bis(tert-butyl)imidazol-2-ylidene (ItBu) or 1,3-bis(tert-butyl)imidazolin-2-ylidene (SItBu). The reduction of aldehydes can be achieved by insertion into the C=O functionality at the C2 (so-called normal) position of the carbene affording zwitterionic products [ItBuCH2 OGaR3 ] (1) or [ItBuCH(p-Br-C6 H4 )OGaR3 ] (2), or alternatively, at its abnormal (C4) site yielding [aItBuCH(p-Br-C6 H4 )OGaR3 ] (3). As evidence of the cooperative behaviour of both components, ItBu and GaR3 , neither of them alone are able to activate any of the carbonyl-containing substrates included in this study NMR spectroscopic studies of the new compounds point to complex equilibria involving the formation of kinetic and thermodynamic species as implicated through DFT calculations. Extension to ketones proved successful for electrophilic α,α,α-trifluoroacetophenone, yielding [aItBuC(Ph)(CF3 )OGaR3 ] (7). However, in the case of ketones and nitriles bearing acidic hydrogen atoms, C-H bond activation takes place preferentially, affording novel imidazolium gallate salts such as [{ItBuH}(+) {(p-I-C6 H4 )C(CH2 )OGaR3 }(-) ] (8) or [{ItBuH}(+) {Ph2 C=C=NGaR3 }(-) ] (12)

    The effect of polyploidy and hybridization on the evolution of floral colour in Nicotiana (Solanaceae)

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    Background and Aims: We investigate whether changes in floral colour accompany polyploid and homoploid hybridisation, important processes in angiosperm evolution. Potentially, changes in floral colour can facilitate speciation through pollinator shifts. Methods: We examined spectral reflectance of corolla tissue from 60 Nicotiana (Solanaceae) accessions (41 taxa) based on spectral shape (corresponding to pigmentation) as well as bee and hummingbird colour perception to assess patterns of floral colour evolution. We compared polyploid and homoploid hybrid spectra to those of their progenitors to evaluate whether hybridisation has resulted in floral colour shifts. Key Results: Floral colour categories in Nicotiana seem to have arisen multiple times independently during the evolution of the genus. Polyploid and homoploid hybrids can display a floral colour: 1) intermediate between progenitors, 2) like one or other progenitor, or 3) a transgressive or divergent colour not present in either progenitor. Conclusions: Floral colour evolution in Nicotiana is weakly constrained by phylogeny, but colour shifts occur and are sometimes associated with allopolyploid or homoploid speciation. Transgressive floral colour in N. tabacum has arisen by inheritance of anthocyanin pigmentation from its paternal progenitor while having a plastid phenotype like its maternal progenitor. Potentially, floral colour evolution has been driven by, or resulted in, pollinator shifts

    New outcomes of Lewis base addition to diboranes(4): electronic effects override strong steric disincentives

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    Two surprising new outcomes of the reaction of Lewis bases with dihalodiboranes(4) are presented, including sp2–sp3 diboranes in which the Lewis base unit is bound to a highly sterically congested boron atom, and a rearranged double base adduct. The results provide a fuller understanding of the reactivity of diboranes, a poorly-understood class of molecule of critical importance to synthetic organic chemistry

    Erratum to: 36th International Symposium on Intensive Care and Emergency Medicine

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    [This corrects the article DOI: 10.1186/s13054-016-1208-6.]

    Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector

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    A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements
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