Oxidative Fluorination of Selenium and Tellurium Compounds using a Thermally Stable Phosphonium SF5 - Salt Accessible from SF6.

Fluorinated group 16 moieties are attractive building blocks in synthetic chemistry but only few synthetic methods are available to prepare them. Herein, we report a new oxidative fluorination reagent capable of stabilizing reactive fluorinated anions. It consists of an SF5 - anion and a chemically inert phosphonium cation and is exceptionally thermally stable. Accordingly, it was used to generate the SeF5 - and TeF5 - anions from the elemental chalcogens and to prepare the unknown tetrafluoro(phenyl)-λ5 -selenate PhSeF4 - and -tellurate PhTeF4 - from the corresponding diphenyl dichalcogenides. In addition, we show that further derivatization of [PhTeF4 ]- by oxidation to trans-PhTeF4 O- and subsequent alkylation gives access to a new class of trans-(alkoxy)(phenyl)tetrafluoro-λ6 -tellanes (trans-PhTeF4 OR), thus providing an approach to introduce the functional group into organic molecules.

Synthesis of N-Heterocyclic Carbenes and Their Complexes by Chloronium Ion Abstraction from 2-Chloroazolium Salts Using Electron-Rich Phosphines.

N-Heterocyclic carbenes (NHCs) are commonly prepared by deprotonation of azolium salts using strong anionic bases. This reaction is often unselective, yielding alkali metal NHC complexes or dimerized NHCs. Alternatively, free NHCs are obtained by the dechlorination of 2-chloroazolium salts using electron-rich phosphines. PPh3 , PCy3 , and PtBu3 are unsuitable for Cl+ abstraction, while the sterically encumbered tris(1,3-tert-butylimidazolidin-2-ylidenamino)phosphine 1 selectively removes Cl+ from 2-chloroazolium salts. Since bulky 1 does not bind to metal complexes, it was used for the preparation of NHC complexes via in situ Cl+ abstraction from 2-chloroazolium salts. The dechlorination was employed for the site-selective monometallation with IrI , IrIII , RhI , RhIII , and RuII of a bis-NHC precursor composed of a 2-chlorobenzimidazolium and a 2-chlorobenzimidazole group, followed by the preparation of the heterobimetallic IrIII /PdII complex [18](BF4 )2 by a dechlorination/oxidative addition reaction sequence.

Bias and comparison framework for abusive language datasets.

Recently, numerous datasets have been produced as research activities in the field of automatic detection of abusive language or hate speech have increased. A problem with this diversity is that they often differ, among other things, in context, platform, sampling process, collection strategy, and labeling schema. There have been surveys on these datasets, but they compare the datasets only superficially. Therefore, we developed a bias and comparison framework for abusive language datasets for their in-depth analysis and to provide a comparison of five English and six Arabic datasets. We make this framework available to researchers and data scientists who work with such datasets to be aware of the properties of the datasets and consider them in their work.

A Size-Flexible Organometallic Box for the Encapsulation of Fullerenes.

A palladium-cornered molecular square with four pyrene-bis(imidazolylidene) bridging ligands is reported. This metallo-polygon can encapsulate C60 and C70 . The X-ray diffraction structures of the empty cage as well as the cages complexed with both fullerenes are described. The fullerene encapsulation produces perturbations in the structural parameters of the metallo-square, showing that it can adjust the shape of its cavity to the size of each fullerene.

T-DNA alleles of the receptor kinase THESEUS1 with opposing effects on cell wall integrity signaling.

Perturbation of cellulose synthesis in plants triggers stress responses, including growth retardation, mediated by the cell wall integrity-sensing receptor-like kinase (RLK) THESEUS1 (THE1). The analysis of two alleles carrying T-DNA insertions at comparable positions has led to conflicting conclusions concerning the impact of THE1 signaling on growth. Here we confirm that, unlike the1-3 and other the1 alleles in which cellular responses to genetic or pharmacological inhibition of cellulose synthesis are attenuated, the1-4 showed enhanced responses, including growth inhibition, ectopic lignification, and stress gene expression. Both the1-3 and the1-4 express a transcript encoding a predicted membrane-associated truncated protein lacking the kinase domain. However, the1-3, in contrast to the1-4, strongly expresses antisense transcripts, which are expected to prevent the expression of the truncated protein as suggested by the genetic interactions between the two alleles. Seedlings overexpressing such a truncated protein react to isoxaben treatment similarly to the1-4 and the full-length THE overexpressor. We conclude that the1-4 is a hypermorphic allele; that THE1 signaling upon cell wall damage has a negative impact on cell expansion; and that caution is required when interpreting the phenotypic effects of T-DNA insertions in RLK genes.