Synthesis of novel salts with HF, AsF3 and XeF2 as ligands to metal cations

A review of all known compounds of the type [Mⁿ(L)_m](AF₆)_n (M is a metal in the oxidation state n; A = P, As, Sb and Bi; L = HF, AsF₃ and XeF₂) is given with the emphasis on the compounds isolated and characterized by our group. The synthetic routes for the preparation of these compounds are given together with a brief analysis of their structures. In the case of L = XeF₂ the influence of the properties of the cation and the anion on the structural diversity of these coordination compounds is discussed. A brief analysis of their Raman spectra is also given.     

Triphenylphosphine-catalyzed isomerization of alkynyl ketones in aqueous solution

An efficient isomerization of alkynyl ketones to(E,E)-diene ketones was developed.The reaction catalyzed by 20 mol% triphenylphosphine in aqueous media gave the desired products in good yields.     

Straightforward synthesis of alkynyl imines via 1,2-elimination of α,α-dichloroketimines

Alkylation of α,α-dichloroketimines at the α-position with benzyl bromides afforded β-arylated α,α-dichloroketimines in good yields. The latter imines could be easily transformed to the corresponding alkynyl imines, a synthetically important class of compounds, via 1,2-elimination of HCl upon treatment with 2 equiv of sodium hydride in DMSO or potassium tert-butoxide in THF.     

三苯基锗烯或炔基膦酸衍生物的合成

由三苯基氯化猪与烯或炔基膦酸盐反应,合成了８种新的三苯基锗烯基或炔基膦酸衍生物,利用元素分析,ＩＲ和ＨＮＭＲ表征了这些化合物的结构     

From magnetic molecules to magnetic solids: An ab initio expertise

The efficiency of ab initio wavefunction based methods is demonstrated using various systems characterized by the presence of open shells. It is recalled that the low-energy spectroscopy of molecular architectures as well as extended materials is accessible and can be rationalized by including in a hierarchical way the valence (i.e. non-dynamical) and dynamical correlation effects. Such methodology not only allows one to investigate vertical transition energies but also gives access to a possible reading of the wavefunction in the ground and excited states.     

Organometallic complexes for nonlinear optics: Part 21. Syntheses and quadratic hyperpolarizabilities of alkynyl complexes containing optically active 1,2-bis(methylphenylphosphino)benzene ligands

The preparation of the chloro complex trans-[FeCl₂{(R,R)-diph}₂] (1) and the alkynyl complexes trans-[M(4-CCC₆H₄R)Cl{(R,R)-diph}₂] [M=Fe, R=NO₂ (2); M=Ru, R=H (4), NO₂ (5), (E)-CH=CH-4-C₆H₄NO₂ (6); M=Os, R=NO₂ (7)], incorporating the optically active diphosphine 1,2-bis(methylphenylphosphino)benzene (diph), are described. Oxidation potentials, as determined by cyclic voltammetry, increase as 2<7<5. Molecular quadratic nonlinearities by hyper-Rayleigh scattering at 1064 nm increase upon introduction of an acceptor group (4<5), chain-lengthening of bridging group (5<6), and proceeding from 3d to 4d and 5d metal (2≤5≤7). Two-level-corrected nonlinearities reproduce the first two trends, but metal variation follows the sequence 2<7<5. The experimental and two-level-corrected nonlinearities for 6 (2795×10⁻³⁰ and 406×10⁻³⁰ esu, respectively), are amongst the largest observed thus far for organometallic complexes. Crystals of complexes 2 and 7 exhibit second-harmonic generation (assessed using the Kurtz powder technique), with an efficiency for the former of twice that of urea.     

Characterization and Molecular Structure of Bis(Isopropyl Xanthate) Bis(1,10-Phenanthroline) Nickel(II): [Ni(phen)2(CH3)2CHOCSS](CH3)2CHOCSS

The crystal and molecular structure of the title compound, [Ni(phen)₂(CH₃)₂CHOCSS](CH₃)₂CHOCSS has been determined by X-ray diffraction. The brown crystal is triclinic of space group Pi, with parameters a = 11.790(2), b = 12.410(3), c = 12.680(3) Å, α = 92.49(3), β = 96.54(3), γ = 117.43(3)° and Z = 2. The compound contains a six-coordinate cation and an isopropyl xanthate anion (CH₃)₂CHOCSS^?, the central Ni atom is chelated by four nitrogen atoms of two phenanthroline ligands and two sulfur atoms of an isopropyl xanthate ligand. The TG data indicate that it decomposed completely at 734°C.     

Study on the interaction between hepatitis B virus functional receptor NTCP and ligands by surface plasmon resonanceEI北大核心CSCD

Sodium/taurocholate cotransporting polypeptideNTCPSLC10A1mediates the entry of hepatitis B virusHBVinto hepatocytes. NTCP is the functional receptor for HBV infection and a potential target for anti-HBV drugs. At presentmethods that evaluate the interaction between NTCP and its ligands are still limited. In this paperthe recombinant NTCP was expressed by Sf9 cells and purifiedand fixed on the surface plasmon resonanceSPRsensor chip by indirect antibody coupling. According to SPR kinetic analysisthe equilibrium dissociation constant KD of HBV PreS1 polypeptide binding to NTCP is 4.93 μµmol/L. The equilibrium dissociation constant KD of classic substrate taurocholate sodium for NTCP is 25.3 μµmol/L. Rather than the inhibition capacity of compounds to block NTCP substrate transportationthe equilibrium dissociation constant measured by SPR method can compare the binding affinity of compounds to NTCPand can be used to develop anti-HBV drugs based on NTCP-PreS1 interaction. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Gold(I) complexes bearing phosphole ligands: Synthesis and antimalarial activity

A series of gold(I)-monophosphole complexes have been synthesized and characterized. The introduction of a nitrogen moiety in the complex structure was envisioned either by choosing the bis(trifluoromethanesulfonyl)imidate ligand as the X-ligand or by preparing a new pyrrolidinophosphole ligand as the L-ligand. All the complexes have been evaluated in vitro for their antimalarial activity. These gold–phosphole complexes showed moderate activities with IC₅₀ values ranging from 9.7 to 24 μM against Plasmodium falciparum chloroquine-resistant strains.     

Supramolecular Assemblies of Phosphorylated Cavitands

The recent results in the chemistry of cavitands have proved that they are very efficient molecular receptors and potential precursors of molecular devices. In this context, we have investigated the synthesis and binding properties of phosphorylated cavitands. The stereoselective synthesis and the structural studies of the new compounds showed that these bowl-shaped molecules possess a well defined aromatic cavity surrounded by four phosphoryl groups (P=O or P=S). They are very efficient ligands for metal and organic cations. They are able to encapsulate cationic species by cooperative effect of the preorganized aromatic cavity and the four phosphorylated groups. Moreover, the upper and lower rim functionalitics can lead to the formation of molecular capsules and supramolecular assemblies whose properties and structures have been investigated by X-ray diffraction and NMR studies in solution.