Visible-light-induced direct oxysulfonylation of alkynes with sulfonyl chlorides and HCl

A mild, practical and efficient strategy to prepare β-keto sulfones has been developed by visible-light-induced reactions. This reaction involved Ir(dtbbpy)(ppy)₂PF₆-catalyzed direct functionalization of alkynes with sulfonyl chloride and HCl using air as the oxidant. HCl not only acted as a hydrogen source in the proton transfer process, but also played a vital role in the reaction process.     

One-pot synthesis of sulfonyl (E)-stilbenes by nitrobenzene-mediated dimerizative desulfonation of benzylic sulfones

A facile one-pot synthetic route for preparing sulfonyl (E)-stilbenes 4 is developed. The efficient route is realized by a nitrobenzene (PhNO₂)-mediated dimerizative desulfonation of benzylic sulfones 3 in the presence of sodium hydride (NaH) in good yields. Some synthetic investigations of sulfonyl stilbenes 4 are also examined.     

TBAI-mediated regioselective sulfenylation of indoles with sulfonyl chlorides in one pot

A versatile method for the synthesis of 3-sulfenylated indoles via TBAI promoted sulfenylation of indoles with sulfonyl chlorides in one pot has been presented. This system features highly regioselective, metal-free, easy operation, and shows a broad functional group tolerance leading to excellent yields. And this reaction could be easily conducted in 10?mmol scale with high effectivity. A plausible mechanism is proposed.     

Convenient synthesis of α,β-unsaturated sulfones via a Mizoroki-Heck reaction of arylboronic acids with phenyl vinyl sulfones

Palladium acetate catalyzed Mizoroki-Heck reaction of arylboronic acids with phenyl vinyl sulfones afford α,β-unsaturated sulfones in good yields.     

Metal-free catalyzed synthesis of the (E)-vinyl sulfones via aromatic olefins with arylsulfonyl hydrazides

Synthesis of vinyl sulfones from aromatic olefins and arylsulfonyl hydrazides via I₂-TBHP catalyzed system under the N₂ atmosphere is described. Owing to no use of metal, only producing N₂ and water as the byproducts and directly available reactants, this reaction could validly avoid many disadvantages of the transition metal catalysts. In addition, the desired product can be collected with moderate to excellent yields under the suitable conditions.     

Lewis acid promoted reaction of tetraalkynylstannanes with acyl chlorides: An effective approach towards alkynyl ketones

Tetraalkynylstannanes were found to be atom-economical nucleophilic reagents for the synthesis of α,β-acetylenic ketones. The scope and some limitations of the method are discussed.     

One-pot approach for the regioselective synthesis of β-keto sulfones based on acid-catalyzed reaction of sulfonyl chlorides with arylacetylenes and water

Reaction of sulfonyl chlorides with arylacetylenes and water in the presence of a catalytic amount of sulfonic acid in THF provided β-keto sulfones in good yields with excellent regioselectivity.     

A practical synthesis of aryl sulfones via cross-coupling of sulfonyl hydrazides with aryltriazenes using copper/ionic liquid combination

A new and efficient approach adopting copper-catalyzed cross-coupling of sulfonyl hydrazides with aryltriazenes has been developed to synthesize aryl sulfones using Brønsted acidic ionic liquid as promoter under ambient conditions. The process employs stable and easy to handle reacting partners, and is endowed with broad substrate scope.     

An efficient palladium-catalyzed coupling reaction of lithium alkynyltriisopropoxyborates with acid chlorides: a new access to synthesis of conjugated ynones

An efficient palladium-catalyzed protocol for the synthesis of ynones from lithium alkynyltriisopropoxyborates with acid chlorides under mild neutral conditions.     

Silver(I) Clusters Stabilized by the Carba-closo-dodecaboranylethynyl Ligand with O-Donor Coligands and Template Ions

Large silver(I) clusters stabilized by the dianionic carba-closo-dodecaboranylethynyl ligand were obtained. Crystallization of polymeric {Ag₂(12-C≡C-closo-1-CB₁₁H₁₁)}_n from dimethyl sulfoxide afforded [Ag₁₄(12-C≡C-closo-1-CB₁₁H₁₁)₇(DMSO)₁₂] · DMSO that contained an Ag^I₁₀ cage augmented by four Ag^I ions. Crystals of [Ag₁₆(12-C≡C-closo-1-CB₁₁H₁₁)₈(THF)₁₂] · 2THF were obtained from anhydrous THF and {Ag₂(12-C≡C-closo-1-CB₁₁H₁₁)}_n. In the presence of moisture the similar but water-containing complex [Ag₁₆(12-C≡C-closo-1-CB₁₁H₁₁)₈(THF)₁₂(H₂O)₂] · 2.5THF was identified. Both silver(I) clusters are composed of a central octahedral Ag^I₆ unit and ten further silver(I) ions bonded via argentophilic interactions. [Ag₁₄(12-C≡C-closo-1-CB₁₁H₁₁)₇(DMSO)₁₂] · DMSO and [Ag₁₆(12-C≡C-closo-1-CB₁₁H₁₁)₈(THF)₁₂] · 2THF were characterized by elemental analysis and vibrational (IR and Raman) as well as NMR spectroscopy. In addition, the crystal structures of [Ag₂₅(12-C≡C-closo-1-CB₁₁H₁₁)₁₂(CH₃CN)_13.5(OH)] · 0.5CH₃CN and [Ag₂₅(12-C≡C-closo-1-CB₁₁H₁₁)₁₂{(CH₃)₂CO}_13.5(H₂O)Cl] · 15(CH₃)₂CO were determined. Both compounds contain Ag^I₁₄ rhombic dodecahedrons augmented by eleven silver(I) ions. A hydroxide or a chloride template ion is present in the center of the rhombic dodecahedron, respectively.     

Silver(I)-mediated coupling reaction of heterocyclic ketene aminals (HKAs) with bis(phenylsulfonyl)sulfides to synthesis of benzenesulfonothioyl-HKAs

An efficient and convenient method was developed for the preparation of 2-benzenesulfonothiol-HKAs via a silver(I)-mediated direct sulfenylation of heterocyclic ketene aminals (HKAs). The method involves a variety of functionalized substrates, leading to α-arylthioyl HKAs in a mild, easy operation, and mild reaction conditions.     

全氟或多氟烷基氯代烷在保险粉引发下与芳香烃 的反应

全氟或多氟烷基氯代烷在保险粉引发下在DMSO溶剂中可以与富电子芳香烃反应,方便地得到氟烷基化的产物。氟烷基化产物的结构和产率主要取决于取代基的供电子能力和位置。     

Gold(I) and Silver(I) Complexes with Thioether Functionalized Silylamido Ligands

The thioether functionalized aminosilanes Me₂Si(NH‐C₆H₄‐2‐SR)₂ (R = Ph, Me) were lithiated with nBuLi and subsequently reacted with AgCl in the presence of PMe₃ or with [AuCl(PMe₃)]. In the case of Me₂Si(NH‐C₆H₄‐2‐SPh)₂ the dinuclear complexes [M₂{Me₂Si(NC₆H₄‐2‐SPh)₂}(PMe₃)₂] (M = Ag; Au) were isolated. The analogous reactions starting from Me₂Si(NH‐C₆H₄‐SMe)₂ afforded the dinuclear gold complex [Au₂{Me₂Si(NC₆H₄‐2‐SMe)₂}(PMe₃)₂] and the tetranuclear silver complex [Ag₄{Me₂Si(NC₆H₄‐2‐SMe)₂}₂(PMe₃)₂]. In the dinuclear compounds of the type [M₂{Me₂Si(NC₆H₄‐2‐SR)₂}(PMe₃)₂], each of the silylamide N atoms is connected to a M(PMe₃) group to give a nearly linear N–M–P arrangement with Ag–N and Au–N bonds in the range of 212.0(4)–213.3(4) pm and 205.3(3)–208.1(9) pm, respectively. [Ag₄{Me₂Si(NC₆H₄‐2‐SMe)₂}₂(PMe₃)₂] consists of a central Si₂N₄Ag₂ ring with linearly coordinated Ag atoms (Ag‐N: 223.1(4)–222.1(4) pm) and two peripheral Ag(PMe₃) units, which are connected to the amido N atoms in a chelating mode. The relatively short transannular Ag ··· Ag separation (277.6(1) pm) within the Si₂N₄Ag₂ ring hints for argentophilic interactions. The peripheral Ag atoms are three coordinated with Ag–N distances of 233.9(4)–242.8(4) pm.     

Synthesis,Structures, and Photophysics of Polynuclear Silver(I) Thiolate and Silver(I) Thiocarboxylate Complexes with Dppm Ligands

Trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes [Ag₃(μ‐dppm)₃(μ_n‐SR)₂](ClO₄) [n = 2, R = C₆H₄Cl‐4 ( 1 ) and C{O}Ph ( 2 ); n = 3, R = tBu ( 3 )], pentanuclear silver(I) thiolate complex [Ag₅(μ‐dppm)₄(μ₃‐SC₆H₄NO₂‐4)₄](PF₆) ( 4 ), and hexanuclear silver(I) thiolate complexes [Ag₆(μ‐dppm)₄(μ₃‐SR)₄]Y₂ [Y = ClO₄, R =C₆H₄CH₃‐4 ( 5 ) and C₁₀H₇ (2‐naphthyl) ( 7 ); Y = PF₆, R = C₆H₄OCH₃‐4( 6 )], were synthesized [dppm = bis(diphenylphosphanyl)methane] and their crystal structures as well as photophysical properties were studied. In the solid state at 77 K, trinuclear silver(I) thiolate and silver(I) thiocarboxylate complexes 1 and 2 exhibit luminescence at 470–523 nm, tentatively attributed to originate from the ³IL (intraligand) of thiolate or thiocarboxylate ligands, whereas hexanuclaer silver(I) thiolate complexes 5 and 7 produce dual emission, in which high‐energy emission is tentatively attributed to come from the ³IL of thiolate ligands and low‐energy emission is tentatively assigned to come from the admixture of metal ··· metal bond‐to‐ligand charge‐transfer (MMLCT) and metal‐centered (MC) excited states.     

Silver(I) N-heterocyclic carbene halide complexes: A new bonding motif

Two new NHC silver halide salts have been synthesised and structurally characterised, and they show the two most common structural forms for such salts: the (NHC)AgX and the forms (both have a stoichiometry of 1 NHC:1 Ag:1 halide). A third new compound has been synthesised and structurally characterised: this compound has an unprecedented 2 NHC:1 Ag:1 halide stoichiometry and exhibits a planar arrangement of two coordinating NHCs, and a coordinating bromide about the central silver. The Ag-Br bond is long in the solid state and, together with solution NMR data, this suggests that a formulation of (NHC)₂Ag⁺Br⁻ might be more appropriate.     

Cis-and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper(II) and Silver(I)

After the preparation of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene(bdib),a nitrogen heterocycle with potential coordination manners of both cis-and tram-configuration forms,three complexes,including successfully self-assembled.Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with P1 space group.     

Macrocyclic‐ligand Induced Synthesis of Aryl Ethynides with Divergent Silver(I) Clusters

Two structurally characterized metal‐cluster‐centered supramolecular architectures named [Ag₈(1,2‐(C ≡ C)₂‐C₆H₄ )( Py[6] )(CF₃CO₂ )₆] · 2.5MeOH ( 1 ) and [Ag₁₂(1,2,4,5‐(C ≡ C)₄C₆H₂ )( Py[6] )₂(CF₃SO₃ )₈]·4MeOH ·3H₂O ( 2 ) are synthesized through the interaction with a bowl‐shaped macrocyclic ligand Py[6] . Particularly, two dissimilar silver(I) clusters are resulted in 2 within the structure under the influence of the macrocyclic ligand Py[6] . Such dissimilarity of the silver(I) cluster is also reflected on the structural and photophysical differences between 1 and 2 .     

AR-Ag(I)体系的共振散射光谱法测定痕量银

在pH=4.4的NaAc-HAc缓冲介质和2.0×10-3mol/L十二烷基苯磺酸钠(SDBS)溶液中,Ag(I)与茜素红(AR)可形成较稳定的离子缔合物微粒,其在324、360和500nm处分别产生3个较强的共振散射峰。在最佳实验条件下,浓度在0.022～2.160μg/mL之间的Ag(I)与共振散射强度ΔI324nm呈较好的线性关系,检测限为0.139ng/mL。据此,建立了一种测定痕量银的共振散射新方法,并将该方法用于废胶片中痕量银的测定。     

The Complexation Reactions of N-methylated Polyamines with Silver(I) in Dimethylsulfoxide

Abstract

The thermodynamic parameters for the complex formation reactions in dimethylsulfoxide (dmso) between Ag(I) and the following polyamines: N,N′-dimethylethylenediamine (dmen), N,N,N′,N′-tetramethylethylenediamine (dmen), N,N″-dimethyl-diethylenetriamine (dmdien) and N,N,N′,N″, N″-pentamethyldiethylenetriamine (pmdien) have been determined by potentiometric and calorimetric techniques at 298 K and 0.1 mol dm^?3 ionic strength (NEt₄ClO₄). Only mononuclear complexes are formed (AgL_j ⁺ j = 1,2) where the ligands act prevalently as chelate agents. All the complexes are enthalpy stabilized whereas the entropy changes counteract the complex formation. The results are discussed in terms of different basicities and steric requirements of both the ligands and the complexes formed.