Novel metalloreagent Cp(CO)2FeP(Se)(OR)2 produced from P-Se bond cleavage in the thermal reaction of [CpFe(CO)2]2 with phosphor-1,1-diselenolates

The reaction of [CpFe(CO)2]2 with NH4Se2P(OR)2 yields a novel reagent Cp(CO)2FeP(Se)(OR)2, which has demonstrated coordination properties at the Se center to form heterometallic clusters as well as reactivity at the Se site toward C-based electrophiles.     

Brønsted acidic ionic liquid–catalyzed tandem trimerization of indoles: An efficient approach towards the synthesis of indole 3,3′-trimers under solvent-free conditions

We have observed the role of 1-butane sulfonic acid-3-methylimidazolium tosylate, [BSMIM]OTs, as an organocatalyst for the tandem type trimerization of indoles to synthesize indole 3,3′-trimers under neat conditions. Using this developed protocol synthesis of indole trimers with various substituted indoles, which are biologically important, has been reported. From the control experiments and literature, a possible mechanism has been proposed via the generation of indolinium cation in the presence of the ionic liquid catalyst. The catalyst has been recycled for several times. The significant advantages of our methodology are clean reaction with very short time, no chromatography for purification, commercially available substrates, neat reaction conditions, and in the absence of metal. Using the protocol, the MDM2-p53 inhibitor has been synthesized in gram scale with high yield.     

The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees

Atomic partial charges are among the most commonly used interpretive tools in quantum chemistry. Dozens of different ‘population analyses’ are in use, which are best seen as proxies (indirect gauges) rather than measurements of a ‘general ionicity’. For the GMTKN55 benchmark of nearly 2,500 main-group molecules, which span a broad swathe of chemical space, some two dozen different charge distributions were evaluated at the PBE0 level near the 1-particle basis set limit. The correlation matrix between the different charge distributions exhibits a block structure; blocking is, broadly speaking, by charge distribution class. A principal component analysis on the entire dataset suggests that nearly all variation can be accounted for by just two ‘principal components of ionicity’: one has all the distributions going in sync, while the second corresponds mainly to Bader QTAIM vs. all others. A weaker third component corresponds to electrostatic charge models in opposition to the orbital-based ones. The single charge distributions that have the greatest statistical similarity to the first principal component are iterated Hirshfeld (Hirshfeld-I) and a minimal-basis projected modification of Bickelhaupt charges. If three individual variables, rather than three principal components, are to be identified that contain most of the information in the whole dataset, one representative for each of the three classes of Corminboeuf et al. is needed: one based on partitioning of the density (such as QTAIM), a second based on orbital partitioning (such as NPA), and a third based on the molecular electrostatic potential (such as HLY or CHELPG).     

Charge‐Transfer‐Induced Fluorescence Quenching of Anthracene Derivatives and Selective Detection of Picric Acid

2,6‐Divinylpyridine‐appended anthracene derivatives flanked by two alkyl chains at the 9,10‐position of the core have been designed, synthesized, and characterized by NMR, MALDI‐TOF, FTIR, and single‐crystal XRD. These anthracene derivatives are able to recognize picric acid (2,4,6‐trinitrophenol, PA) selectively down to parts per billion (ppb) level in aqueous as well as nonaqueous medium. Fluorescence emission of these derivatives in solution is significantly quenched by adding trace amounts of PA, even in the presence of other competing analogues, such as 2,4‐dinitrophenol (2,4‐DNP), 4‐nitrophenol (NP), nitrobenzene (NB), benzoic acid (BA), and phenol (PH). The high sensitivity of these derivatives toward PA is considered as a combined effect of the proton‐induced intramolecular charge transfer (ICT) as well as electron transfer from the electron‐rich anthracene to the electron‐deficient PA. Moreover, visual detection of PA has been successfully demonstrated in the solid state by using different substrates.     

Synthesis, catalytic activity and phytotoxicity of a supported nickel(II) Schiff base complex

A supported Ni(II) complex has been synthesized and characterized by FTIR, UV–vis diffuse reflectance spectroscopy, thermogravimetric analysis and scanning electron microscopy. Its catalytic activity was evaluated for alkyne–azide coupling and benzothiazole synthesis. These reactions were found to require mild conditions, reaction times, and most importantly, could be carried out in aqueous medium. The catalyst could be easily recovered and reused five times without significant decrease in its activity. Leaching tests indicated that the catalyst is truly heterogeneous. The nickel complex was tested for its inhibition of germination of MTU 7029 seeds. Rice (MTU 7029, Oryza sativa) is a staple crop in southeast Asia.     

Inner-shell single and double ionization potentials of aminophenol isomers

A comprehensive study of single and double core ionization potentials of the aminophenol molecule is reported. The role of relaxation, correlation, relativistic, and basis set effects in these potentials is clarified. Special attention is paid to the isomer dependence of the single and double core ionization potentials. Some of them are also compared with the respective values of the phenol and aniline molecules. It is shown that the core level single ionization potentials of the para-, meta-, and ortho-aminophenol molecules differ only slightly from each other, rendering these structural isomers challenging to distinguish for conventional x-ray photoelectron spectroscopy. In contrast, the energy needed to remove two core electrons from different atoms depends noticeably on the mutual arrangement and even on the relative orientations of the hydroxyl and amine groups. Together with the electrostatic repulsion between the two core holes, relaxation effects accompanying double core ionization play a crucial role here. The pronounced sensitivity of the double ionization potentials, therefore, enables a spectroscopic characterization of the electronic structure of aminophenol isomers by means of x-ray two-photon photoelectron spectroscopy.     

Synthesis and evaluation of deep cavity imidazolyl calix[n]arenes

A series of deep cavity diphenyl imidazolyl calix[n]arenes (4, 6, 8) have been obtained from readily available starting materials through a five step synthetic methodology involving appropriate alkylation of lower rim of preformed calixarene, formylation of the upper rim and subsequent condensation with aryl diketones in the presence of ammonium acetate and glacial acetic acid. Optimized reaction conditions for obtaining the titled derivatives in their cone configuration and their characterization by spectroscopic methods (IR, UV, NMR and FAB mass) have been delineated. The synthesized imidazolyl calixarenes have preliminarily been examined for selective recognition of monovalent metal ions (Li⁺, Na⁺, K⁺, Cs⁺, Ag⁺).     

A "reactive" ratiometric fluorescent probe for mercury species

A ratiometric fluorescent probe for mercury species is developed based on the metal-promoted hydrolysis of a vinyl ether derivative of 2-(benzothiazol-2-yl)phenol in a buffer solution. The probe responds selectively to mercury species over various other metal ions with a marked fluorescence change from blue to cyan through the excited state intramolecular proton transfer (ESIPT) process. The fluorescence titration is complete with 0.5 equiv of HgCl(2), which indicates that the probe also responds to organomercury species, RHgCl.     

Efficient Synthesis of Methyl 6-(6-Aryl-1,2,4-triazin3-yl)pyridine-2-carboxylates

Russian Journal of Organic Chemistry - Methyl 6-(6-aryl-1,2,4-triazin-3-yl)pyridine-2-carboxylates were synthesized in up to 70% yield by one-step condensation of substituted...     

Direct Umpolung Morita–Baylis–Hillman like α‐Functionalization of Enones via Enolonium Species

Herein we report on the umpolung of Morita–Baylis–Hillman type intermediates and application to the α‐functionalization of enone C?H bonds. This reaction gives direct access to α‐chloro‐enones, 1,2‐diketones and α‐tosyloxy‐enones. The latter are important intermediates for cross‐coupling reaction and, to the best of our knowledge, cannot be made in a single step from enones in any other way. The proposed mechanism is supported by spectroscopic studies. The key initial step involves conjugate attack of an amine (DABCO or pyridine), likely assisted by hypervalent iodine acting as a Lewis acid leading to formation of an electrophilic β‐ammonium‐enolonium species. Nucleophilic attack by acetate, tosylate, or chloride anion is followed by base induced elimination of the ammonium species to give the noted products. Hydrolysis of α‐acetoxy‐enones lead to formation of 1,2‐diketones. The α‐tosyl‐enones participate in Negishi coupling reactions under standard conditions.