Scheme3.ReactionofP hI(OAc) 2 with two TMS-OTf stoppingatP hI(OTf)(OAc). Scheme4.ReactionofP hI(OAc) 2 with 2-oxazolines in the presence of two TMS-OTf,which was proposedtop roceed via PhI(OTf) 2 as an intermediate.

It has been previously proposed that pyridines can activate PhICl2 by displacing a chloride and forming the [PhI(Pyr)(Cl)]+ cation as a reactive intermediate. Here we show that pyridine does not...

A study on the potential activating role of pyridine in the electrophilic chlorination of anisole by PhICl2 has led to the discovery that soluble sources of chloride ions activate PhICl2...

The weakly coordinating [B₁₂Cl₁₂]^2- originates from a family of carboranes typically reserved for application in coordination chemistry. Here, we show its readily accessible Ag(I) salt, [Ag]₂[B₁₂Cl₁₂], can be used as a catalyst in the PhICl₂ mediated chlorination of arenes, alkenes, and alkynes. The promising activity displayed by [Ag]₂[B₁₂Cl₁₂] over a variety of commercially available Ag(I) sources merits its incorporation to the toolkit of commonly screened silver catalysts in synthesis.

The weakly coordinating [B₁₂Cl₁₂]^2- originates from a family of carboranes typically reserved for application in coordination chemistry. Here, we show its readily accessible Ag(I) salt, [Ag]₂[B₁₂Cl₁₂], can be used as a catalyst in the PhICl₂ mediated chlorination of arenes, alkenes, and alkynes. The promising activity displayed by [Ag]₂[B₁₂Cl₁₂] over a variety of commercially available Ag(I) sources merits its incorporation to the toolkit of commonly screened silver catalysts in synthesis.

The weakly coordinating dianion [B 12 Cl 12 ] 2À originates from a family of carboranes typically reserved for application in coordination chemistry. Herein, we show that its readily accessible Ag(I) salt, [Ag] 2 [B 12 Cl 12 ], can be used as a catalyst in the PhICl 2 mediated chlorination of arenes, alkenes, and alkynes. The promising activity displayed by [Ag] 2 [B 12 Cl 12 ] over a variety of commercially available Ag(I) sources merits its incorporation to the toolkit of commonly screened silver catalysts in synthesis.

I(iii) reagent [PhI(Pyr)2]2+ (Weiss’ reagent) can be activated with borane Lewis acids in which a pyridine ligand is abstracted giving a more reactive derivative of the reagents.

<div>It has been previously proposed that pyridines can activate PhICl2 by displacing a chloride and forming the [PhI(Pyr)(Cl)]+ cation as a reactive intermediate. Here we show that pyridine does not displace chloride, but rather forms a weak complex with the iodine via halogen bonding along the C-I bond axis. This interaction is investigated by NMR, structural, charge density and theoretical investigations, which all indicate the pyridine does not activate PhICl2 as proposed.</div><div><br></div>