PhICl₂ is activated by chloride ions

Abstract

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...

On the potential intermediacy of PhIBr2 as a brominating agent

“…5,6 On standing in solution or at room temperature, PhICl 2 degrades into PhI and Cl 2 , which in solution occurs over a matter of hours. 7 PhIF 2 and related derivatives (most often with tolyl as the aryl group) are commonly used as a fluorinating agents. [8][9][10] PhIF 2 derivatives are somewhat less convenient to synthesize compared to PhICl 2 , and are also reactive with borosilicate glass.…”

Electrophilic activation of molecular bromine mediated by I(iii)

“…3 Addition of chloride ions was found to effectively catalyze the release of Cl 2 from PhICl 2 via an as-yet undetermined mechanism. 4…”

ArI(NTf2)2: the boundary of oxidative capacity for ArIL2?

“…11 NO 2 –C 6 H 4 –I(OTf) 2 proved to be highly reactive, capable of performing transformations that other ArIL 2 species are incapable of, including the oxidation of cyclohexenes to aromatic rings and direct sp 3 C–H and C–F functionalization. 12 We hypothesized that use of an even more weakly coordinating ligand could further enhance the potential reactivity of the I( iii ) and targeted using bistriflimide (NTf 2 ) as the ligand as the next step. While we were undertaking this study Periana and co-workers isolated and spectroscopically characterized C 6 F 5 –I(NTf 2 ) 2 and showed that at elevated temperatures and pressures direct C–H activation of simple alkanes is possible.…”

“…The most remarkable reaction observed thus far is the rapid, low temperature oxidation of cyclohexene rings into aryls. 12 NO 2 –C 6 H 4 –I(OTf) 2 can oxidize terpenes to p -cymene, a relatively facile oxidation, but also cyclohexene itself to benzene in a 4-electron oxidation using 2 equivalents of NO 2 –C 6 H 4 –I(OTf) 2 . While benzene is a trivial compound, this direct oxidation typically requires high temperatures, long reaction times and a Pd oxide catalyst using molecular O 2 as the oxidant.…”

“…23 We have observed experimentally that NO 2 –C 6 H 4 –I(OTf) 2 is a powerful fluoride abstraction agent, capable of abstracting fluoride from fluoroadamantane. 12 In silico abstraction also occurs from PF 6 − , albeit less completely, but the fluoride becomes more strongly associated with the iodine, with an I–F bond of 201 pm and the geometry of the phosphorane becoming highly distorted (Fig. 3).…”