Three diaryliodonium tetrachloroaurates(III), [Ar1IAr2][AuCl4] (Ar1/Ar2 = Ph/Ph (1), Ph/Mes (2), o-(C6H4)2 (3)), were obtained as solids (62–80%) by the metathetical reaction of [Ar1IAr2](CF3CO2) and H[AuCl4]. In particular, single-crystal X-ray diffraction studies 1–3 revealed three-center bifurcated C–I···(Cl–Au–Cl) halogen bond (XB) more conventional interionic two-center C–I···Cl–Au XB. An XB with iodine(III) center a cation can be formed even when ∠(C–I···X) is much less than 180°...

The reactivity of [Ar¹Ar²I](SCN) toward the solid-state arylation depends on preorganization halogen bond (XB)-bound SCN⁻: <italic>N</italic>-XB-bound thiocyanates, which, in contrast to <italic>N</italic>,<italic>S</italic>-XB-bound, undergoes extremely rare <italic>N</italic>-arylation SCN⁻.

The dibenziodolium cation displays high catalytic activity for the Knorr-type reactions <italic>via</italic> binding with carbonyl O atom.

Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The filled with disordered water molecules which can be reversibly removed on heating. Consistent the remarkable strength and directionality halogen bonds (XBs) driving crystal packing formation, porous structure is stable fully preserved almost quantitative removal readsorption water. systems...

Five new copper(I) complexes─composed of the paired dibenzohalolium and [CuL2]− (L = 1,2,4-oxadiazolate) counterions in which O,O-atoms anion are simultaneously linked to halogen atom─were generated isolated as solid via three-component reaction between [Cu(MeCN)4](BF4), sodium 1,2,4-oxadiazolates, triflates (or trifluoroacetates). This is different from previously reported CuI-catalyzed arylation 1,2,4-oxadiazolones by diaryliodonium salts. Inspection solid-state X-ray structures complexes...

The crystal structure of the newly synthesized 4-methoxyphenyl(phenyl)iodonium thiocyanate, [PhI(4-C6H4OMe)](SCN), represents first example 16-membered cyclic heterooctamer formed by halogen bonding between iodonium cation and SCN−. Results density functional theory (DFT) calculations followed topological analysis electron distribution within framework quantum atoms in molecules (QTAIM) method at ωB97XD/DZP-DKH level reveal that energies attractive intermolecular noncovalent interactions...

Synthesis and X-ray characterization of the four diaryliodonium tetrachloroplatinates(II) [Ar1Ar2I]2[PtCl4] (Ar1/Ar2 = Ph/Ph (1), 4-Cl-C6H4/2,4,6-(MeO)3C6H2 (2), 4-Me-C6H4/2,4,6-(MeO)3C6H2 (3), Ph/2,4,6-(MeO)3C6H2 (4)) allowed deterimination several types unconventional halogen-bond (HaB) patterns. The first example a metal-involved trifurcated four-center μ3-X···(X′,X′,M) HaB is represented by metal-involving I···Pt (the structure 4) with iodonium cations acting as donors, which supported...

A single-crystal X-ray diffraction (XRD) study of diaryliodonium tetrachloroaurates (or, in the recent terminology, tetrachloridoaurates), [(p-XC6H4)2I][AuCl4] (X = Cl, 1; Br, 2), was performed for 1 (the structure is denoted as 1a to show similarity with isomorphic 2a) and two polymorphs─2a (obtained from MeOH) 2b (from 1,2-C2H4Cl2). Examination XRD data these three structures revealed 2-center C-X···AuIII Cl Br) 3-center bifurcated C-Br···(Cl-Au) halogen bonding (abbreviated XB) between...

The structure-directing "key-to-lock" interaction of double σ-(I

Herein, we developed a new synthetic approach for the preparation of N-arylated 1,2,4-oxadiazin-5(6H)-ones by direct arylation with diaryliodonium salts. The reaction symmetrical salts using CuI as catalyst proceeded in toluene presence DIPEA at 60 °C formation desired products isolated yields 46 to 97% (20 examples). use more readily available unsymmetrical required higher temperatures (up 100 °C) achieve similar yields. only limitation observed was an ortho-substituted iodonium salt. In...

Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion light to chemical energy at room temperature. However, the mechanistic insights interaction between plasmon and molecules is still under debate. Herein, we proposed comprehensive study plasmon-assisted reaction mechanism using unsymmetric iodonium salts (ISs) as an probe. The experimental theoretical analysis allow us exclude possible thermal effect or hot electron transfer. We found that with...

Abstract Here, we report the method for copper‐catalyzed N‐arylation of diverse oxadiazolones by diaryliodonium salts under mild conditions in high yields (up to 92%) using available CuI as a catalyst. The developed allows utilizing both symmetric and unsymmetric bearing auxiliary groups such 2,4,6‐trimethoxyphenyl (TMP). We found that steric effects aryl moieties determined chemoselectivity N‐ O‐arylation 1,2,4‐oxadiazol‐5(4 H )‐ones. Mesityl‐substituted demonstrated potential selective...

A facile synthesis of diaryliodonium salts utilizing Oxone as versatile and cheap oxidant has been developed. This method shows wide applicability can be used for the preparation iodonium containing electron-donating or electron-withdrawing groups in good yields. In addition, this procedure applied to symmetric directly from arenes via a one-pot iodination-oxidation sequence.

The simultaneous binding of a molecular entity through two interactions is frequently pursued recognition mode due to the advantages it offers in securing self-assembly. Here, we report how planarity benzothienoiodolium (BTI) cation allows for preorganizing plane hydrogen, halogen, and chalcogen bonds (HBs, XBs, ChBs, respectively) formed by phenyl iodolium iodine, thienyl sulfur. Crystallographic analyses some BTI salts show this interaction coplanarity enables their coupling point toward...

A new powerful hypervalent iodine(<sc>v</sc>) oxidant, a ditriflate derivative of 2-iodoxybenzoic acid (IBX), was prepared by the reaction IBX with trifluoromethanesulfonic and characterized single crystal X-ray crystallography.

We developed an atom- and reaction mass efficient strategy for the preparation of diarylselenides using iodonium salts as reactants. The approach allows obtaining from corresponding trimethoxyphenyl-substituted via a two-step one-pot sequence. proposed metal-free methodology is based on involvement both aryl groups diarylation.

Flow chemistry is considered to be a versatile and complementary methodology for the preparation of valuable organic compounds. We describe straightforward approach synthesis iodonium trifluoroacetates through direct oxidation iodoarenes in simple flow reactor using an Oxone‐filled cartridge. Optimization has been carried out Nelder–Mead algorithm. The procedure allows wide range salts prepared from starting materials.

A straightforward synthesis of diaryliodonium salts is achieved by using Oxone as the stoichiometric oxidant. Slow addition key to obtaining good yields and purities reaction products, which are highly useful reagents in many different areas organic synthesis.

New substituted 1‐arylbenziodoxolones were prepared and their reactivity with azide anion as a nucleophile was investigated. It found that independent of the presence substituents, all reactions proceed nucleophilic substitution iodonium leaving group in electron‐deficient benziodoxolone benzene ring. The bulky substituents ortho position aryl ring slows reaction down, while moderately electron‐withdrawing bromine substituent para to iodine atom increases rate substitution. strongly nitro...

Two diphenyliodonium tetracyanidometallates, [Ph2I]2[M(CN)4] (M = Ni and Pd), were prepared through anion metathesis. Their X-ray structural analyses show that the structure-defining contact for both crystals is charge-assisted I···N halogen bond (HaB) formed between I atom of iodonium cations N atoms CN– ligands. These HaBs assemble bidentate 90°-orienting HaB donor Ph2I+ tetradentate, square planar, 90/180°-orienting acceptors [M(CN)4]2– into supramolecular rectangles, which further...

The supramolecular dimensionality of halogen bonded architectures formed in the solid state by diaryliodonium salts is greater when anion a disulfonate rather than monosulfonate. Specifically, cations conventionally function as double-σ-hole bond (XB) donors and form 0D-heterotetrameric motifs paired with monosulfonate anions. Here it reported that 1,5- 2,6-naphthalenedisulfonate anions are used ditopic XB acceptors, their assemblies provide higher dimensionality. 1,5-Naphthalenedisulfonate...

The arylation of azaheterocycles can be considered as one the most important processes for preparation various biologically active compounds.

We designed 0D, 1D, and 2D supramolecular assemblies made of diaryliodonium salts (functioning as double σ-hole donors) carboxylates (as acceptors). The association was based on two charge-supported halogen bonds (XB), which occurred between IIII sites the iodonium cations carboxylate anions. sequential introduction carboxylic groups in aryl ring benzoic acid added a dimension to 0D organization benzoate, furnished 1D-chained 2D-layered structures when terephthalate trimesate anions,...

The structure-directing “key-to-lock” interaction of double -(I(III))-hole donating iodonium cations with the O-flanked pseudo-lacune rims [β-Mo8O26]4– gives halogen-bonded iodonium–beta-octamolybate supramolecular associates. In occurrence their tetragonal pyramidal motifs, deep and broad -(I(III))-holes a cation recognize molybdate backbone, which provides an electronic pool localized around two lacunes. I∙∙∙O linkages in structures were thoroughly studied computationally classified as...