Abstract:A revised bonding model for diarylhalonium salts, that involves partial s-orbital contribution, provides new insight into periodic trends in structure and reactivity.
“…2). Since it has been shown theoretically and experimentally that cyclic dibenzohalolium cations (7-9) exhibit a higher Lewis acidity and catalytic activity than their acyclic analogues, namely diarylhalonium cations Ar 2 X + , 51,54,71 in this study we focused on the cyclic derivatives 1-9. Cations 1-3 represent pnictonium(V) derivatives, whereas species 4-6 are the representative examples of sulfonium, selenonium, and telluronium cations, respectively.…”
Section: Selected Organoelement Species and Analysis Of Their Electro...mentioning
confidence: 99%
“…[40][41][42][43][44][45][46][47][48][49][50][51] It is worth mentioning that diarylbromonium salts (F; X = Br) have also been reported to exhibit high catalytic activity. [52][53][54][55] Organocatalysts based on ChB donors have gained increasing attention over the last five years. [56][57][58][59][60][61][62][63][64] A series of publications give unambiguous evidence that the catalytic activity of ChB donating species shows a trend similar to that of XB donors, namely the catalytic activity gradually increases from S to Te, and it is higher for cationic species compared to uncharged chalcogen-containing compounds.…”
Section: Introductionmentioning
confidence: 99%
“…40–51 It is worth mentioning that diarylbromonium salts ( F ; X = Br) have also been reported to exhibit high catalytic activity. 52–55…”
This theoretical study sheds light onto the relative catalytic activity of pnictonium, chalconium, and halonium salts in the reactions involving elimination of the chloride and electrophilic activation of the carbonyl...
“…2). Since it has been shown theoretically and experimentally that cyclic dibenzohalolium cations (7-9) exhibit a higher Lewis acidity and catalytic activity than their acyclic analogues, namely diarylhalonium cations Ar 2 X + , 51,54,71 in this study we focused on the cyclic derivatives 1-9. Cations 1-3 represent pnictonium(V) derivatives, whereas species 4-6 are the representative examples of sulfonium, selenonium, and telluronium cations, respectively.…”
Section: Selected Organoelement Species and Analysis Of Their Electro...mentioning
confidence: 99%
“…[40][41][42][43][44][45][46][47][48][49][50][51] It is worth mentioning that diarylbromonium salts (F; X = Br) have also been reported to exhibit high catalytic activity. [52][53][54][55] Organocatalysts based on ChB donors have gained increasing attention over the last five years. [56][57][58][59][60][61][62][63][64] A series of publications give unambiguous evidence that the catalytic activity of ChB donating species shows a trend similar to that of XB donors, namely the catalytic activity gradually increases from S to Te, and it is higher for cationic species compared to uncharged chalcogen-containing compounds.…”
Section: Introductionmentioning
confidence: 99%
“…40–51 It is worth mentioning that diarylbromonium salts ( F ; X = Br) have also been reported to exhibit high catalytic activity. 52–55…”
This theoretical study sheds light onto the relative catalytic activity of pnictonium, chalconium, and halonium salts in the reactions involving elimination of the chloride and electrophilic activation of the carbonyl...
“…The relative binding energies are also in line with the recent experimental measurements of Stuart and co-workers, using neutral Lewis bases. [24] As mentioned, SAPT analyses shed some light on the differences between these three cases (see Figure 8). The dispersion term differences are marginal compared to the other terms.…”
Section: Resultsmentioning
confidence: 79%
“…[13], [14] As bromolium catalysts sometimes outperformed iodolium ones, X the order in Lewis acidity remained unclearuntil very recently, when Stuart and co-workers reported insights on the nature of bonding and behavior of these diarylhalonium ions. [24] Herein, we aim to finally elucidate the origin of the higher Lewis acidity of iodolium vs. diaryliodonium salts via an in-depth analysis of the hybridization of these species and via energy decomposition analyses. The latter tool is also employed to gain additional insights into the effects governing the relative Lewis acidities of the three higher halolium salts.…”
Cyclic diaryliodonium compounds like iodolium derivatives have increasingly found use as noncovalent Lewis acids in the last years. They are more stable than acyclic systems and are markedly more Lewis acidic. Herein, this higher Lewis acidity is analyzed and explained via quantum-chemical calculations and energy decomposition analyses. Its key origin is the change in energy levels and hybridization of iodine’s orbitals, leading to both more favorable electrostatic interaction and better charge transfer. Both of the latter seem to contribute in similar fashion, while hydrogen bonding as well as steric repulsion with the phenyl rings play at best a minor role. In comparison to iodolium, bromolium and chlorolium are less Lewis acidic the lighter the halogen, which is predominantly based on less favorable charge-transfer interactions.
In this study, we explored the reactivity of meta‐trifluoromethanesulfonate (OTf) substituted diaryliodonium salts under alkaline conditions. Two distinct pathways with direct arylation of pyrrole derivatives and Diels‐Alder cycloaddition via aryne intermediates, have been found upon the relative alkalinity strength of potassium carbonates or hydroxides. This approach offers a straightforward and efficient route to synthesize heterocyclic aromatics under mild reaction conditions with tolerance of various functional groups.
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