Synthesis, Characterization, and Reaction of a Both Inter‐ and Intramolecularly Coordinated Pseudocyclic Iodosylbenzene–Trifluoroacetic Acid Complexes

Abstract

An ortho‐substituted ether‐oxygen‐coordinated pseudocyclic iodosylbenzene‐trifluoroacetic acid (pcISB‐TFA) complex was synthesized and characterized by X‐ray crystallographic analysis. TFA suppresses the disproportionation by both coordination of the oxygen atom to the iodine(III) center through secondary bonding and by hydrogen bonding to the oxygen anion. This bench‐stable reagent is highly soluble in common organic solvents and reacts with various organic substrates under mild reaction conditions to give the corresponding products in good yields.

Supramolecular Aggregation of Perfluoroorganyl Iodane Reagents in the Solid State and in Solution

“…Typically, the iodane reagents exhibit significant Lewis acidity, which has been traced back to a σ hole at the iodine atom . This finding agrees well with the crystal structures of many oxygen‐containing compounds of trivalent iodine, in which the fourth coordination site is occupied by short I ··· O contacts to adjacent molecules . Thereby, a square‐planar coordination of the iodine atom is highly favored and can be compared with the coordination geometries of structurally related metal compounds such as gold(III) complexes.…”

“…1 [1] [3] 226.7(3) 211.8 (2) 169.78 (7) 299.8(1) 5 [6] 229.9(2) 211. 8 As anticipated, the crystal structures of 1-9 go beyond simple monomeric molecules, and intermolecular I···O contacts far shorter than the sum of the van der Waals radii of I and O (350 pm) [17] were found in all compounds. In the acid reagents 1-3, the iodine atoms display pseudo-square-planar coordination resulting from the chelating coordination of the carboxy moiety of an adjacent molecule, which results in shorter [302.1(3)-309.8(2) pm] and longer [310.1(2)-327.3(2) pm] I···O contacts.…”

“…[14] This finding agrees well with the crystal structures of many oxygen-containing compounds of trivalent iodine, in which the fourth coordination site is occupied by short I···O contacts to adjacent molecules. [15][16][17] Thereby, a square-planar coordination of the iodine atom is highly favored and can be compared with the coordination geometries of structurally related metal compounds such as gold(III) complexes. In the latter, the Au atom displays square-planar coordination with four ligands, but the fifth and sixth coordination site are additionally readily occupied in the crystalline state through secondary bonding interactions with free donor moieties (Scheme 2a).…”

Transition‐Metal‐Free Synthesis of Phenanthridinones through Visible‐Light‐Driven Oxidative C–H Amidation

“…The product was afforded as a paleyellow oil. R f = 0.56 (9 % EtOAc in n-Hexane) 1 [15] General Procedure for the Synthesis of Methyl 2-Iodobenzoate 2-iodobenzoic acid (6.2 g, 25.0 mmol, 1.0 equiv.) was taken up in concentrated H 2 SO 4 (50 mL), and heated to 60°C (oil bath).…”

“…The residue was purified by column chromatography to afford methyl 5-bromo-2-iodobenzoate (79 %, 6.7 g, 2 steps). [15] General Procedure for the Suzuki-Miyaura Cross-coupling: A flask was refilled with argon. The boronic acids (1.1 equiv.…”