Hexaphenylditetrels – When Longer Bonds Provide Higher Stability

We present a computational analysis of hexaphenylethane derivatives with heavier tetrels comprising the central bond. In stark contrast to parent hexaphenylethane, the heavier tetrel derivatives can readily be prepared. In order to determine the origin of their apparent thermodynamic stability against dissociation as compared to the carbon case, we employed local energy decomposition analysis (LED) and symmetry-adapted perturbation theory (SAPT) at the DLPNO-CCSD(T)/def2-TZVP and sSAPT0/def2-TZVP levels of theory. We identified London dispersion (LD) interactions as the decisive factor for the molecular stability of heavier tetrel derivatives. This stability is made possible owing to the longer (than C−C) central bonds that move the phenyl groups out of the heavily repulsive regime so they can optimally benefit from LD interactions.     

A Facile Route to the Synthesis of New 2,3-Disubstituted Benzocoumarins

Triphenylphosphine catalyzes the reaction between 2-hydroxy-1-naphthaldehyde and π-deficient acetylenes to give the newly prepared benzo[f]chromenes. The mechanism for the formation of products is discussed.     

Corrigendum to: on the inheritance of the strongly π-extending property

In this corrigendum, we provide correct versions of Theorem 2.8 and Corollary 3.2, retract two consequences of the previous form of the Theorem 2.8. To this end, the main results of the article remain after the aforementioned changes.     

A cinnamoyl substituted Nile Red-based probe to detect hydrazine

Herein we discovered that a Nile Red-based probe with a cinnamoyl unit was highly selective and sensitive to N₂H₄. Hydrazinolysis by N₂H₄ would release a hydroxyl substituted Nile Red and result in remarkable fluorescence quench. Importantly, Cys/Hcy would not interrupt the N₂H₄ recognition. This is because, for this probe, the combination of the π-π conjugate system can stabilize the ethylene union, which results in the nucleophilic addition of the thiol group of Cys/Hcy becomes non-effective.     

Synthesis,Redox Properties,and Electronic Spectra of Sterically Crowded Triarylphosphines Conjugated with Electron Acceptors

Abstract

Synthesis, redox properties, and electronic spectra of the sterically crowded triarylphosphines conjugated with π-electron systems, especially electron acceptors such as carbonyl group, are briefly reviewed. The sterically crowded triarylphosphines conjugated with various π-electron systems were synthesized from the common synthetic intermediate, (bromoaryl)phosphine, by conventional manner. The sterically crowded triarylphosphines conjugated with the electron acceptors exhibit visible absorption and fluorescence with large Stokes shift. Large solvent effect, redshift in polar solvent, and good correlation with the difference of the oxidation potential of the phosphine moiety and the reduction potential of the acceptor moiety suggest polar excited state resulting from HOMO-LUMO transition.     

Toward Metathesis Reactions on Vinylphosphaalkenes

Abstract

Attempts to utilize C-ethylenic phosphaalkenes in metathesis reactions are discussed. Unprecedented reactivity is observed where the vinylphosphaalkene undergoes the first step of the catalytic cycle and cross-metathesis with the phenylmethylene moiety of Grubbs 2nd generation catalyst. However, homo-metathesis reaction to form 1,6-diphosphahexa-1,3,5-triene is not observed, presumably due to steric constraints.     

Alternative Synthesis of A C,C-Diacetylenic Phosphaalkene

Abstract

Bis(trimethylsilyl)-terminated C,C-diacetylenic phosphaalkene was prepared from Mes*PCl₂ and a propargylic Grignard reagent that in turn was formed from 3-bromo-1,5-bis(trimethylsilyl)penta-1,4-diyne and Rieke-Mg.     

New π-Extended Donors: Synthesis,Characterization, Electrochemical and Electrical Conductivity Studies

A new series of tetrathiafulvalene (TTF) molecules with extended π-system was prepared by using a Wittig reaction to generate the TTF key. The process of deprotection-alkylation of thiolates provided access to a wide variety of molecules. The study of their reducing power was carried out by cyclic voltammetry. Charge transfer complexes have also been chemically prepared by using TCNQ as an electron acceptor; the electrical conductivity of their compressed powders shows insulator behavior. The IR spectra of the TCNQ salts were recorded and used to characterize and estimate the degree of charge transfer of these complexes.

GRAPHICAL ABSTRACT      

Calixarenes as Polyhapto-aromatic Ligands: Alkali Metal Ions and Sulfonated Calixarenes

Crystal structure determinations for the hexarubidium and octacesium derivatives of calix[6]arene hexasulfonic acid, as well as of a new solvate of the pentasodium derivative of calix[4]arene tetrasulfonic acid, and comparison with structural data from the literature for alkali metal complexes of sulfonated calixarenes, have provided further evidence for the importance of interactions with aromatic ~ -electrons for the heavier alkali metal cations. There is evidence as well that this interaction can be enhanced by extended ionization of the sulfonated calixarene.     

Removal of carbonyl sulfide from CO2 stream using AgNO3-modified NaZSM-5

Removal of carbonyl sulfide (COS) from CO₂ stream is significant for the production and utilization of food grade CO₂. This study investigates the adsorption performance of Ag/NaZSM-5 as adsorbent prepared by incipient wetness impregnation for the removal of COS from a CO₂ stream in a fixed-bed adsorption apparatus. Effects of various conditions on the preparation of adsorbent, adsorption and desorption were intensively examined. The results revealed that COS can be removed to below 1×10^?9 from a CO₂ stream (1000 ppm COS/CO₂) using Ag/NaZSM-5 (10 wt% AgNO₃) with an adsorption capacity of 12.86 mg-g^?1. The adsorbent can be fully regenerated using hot air at 450 °C. The adsorption ability remained stable even after eight cycles of regeneration.