An examination of the structures of iodosylbenzene (PhIO) and the related imido compound, PhINSO₂-4-Me-C₆H₄, by X-ray powder diffraction and EXAFS (extended X-ray absorption fine structure) spectroscopy

Abstract

Structural data derived from X-ray powder diffraction and EXAFS spectroscopy are presented for iodosyl benzene (PhlO) and the imido analogue, PhlNS02-4-Me-C6H4, which indicate that these compounds are polymeric in the solid state.

Spectral, electrochemical, and catalytic properties of a homologous series of manganese porphyrins as cytochrome P450 model: The effect of the degree of β-bromination

“…PhIO, which is polymeric in nature [84], is the classical oxygen donor in these systems, but a closely related oxidant, PhI(OAc) 2 , has been receiving considerable attention recently, as an in situ source of monomeric PhIO that reacts promptly with the Mn-porphyrin [39] with minimal formation of the PhIO disproportionation products, PhI and PhIO 2 [85]. The true nature of the coordination sphere of the Mn center at the rate-limiting step of the catalytic oxidation by different oxygen donors has been questioned by Collman et al [43], who concluded that the active species generated from PhIO and PhI(OAc) 2 were different.…”

Ventricular septal rupture masquerading as coronary perforation during intervention for acute myocardial infarction

“…Commercially available iodosylbenzene (PhIO) 1 , a pale yellow amorphous powder, is a versatile oxygen atom transfer agent in organic and biomimetic syntheses 1. A µ‐oxo‐bridged polymeric structure of iodosylbenzene 1 with a secondary I ··· O hypervalent bonding of 2.377(12) Å has been deduced from X‐ray powder diffraction and extended X‐ray absorption fine structure analysis (Scheme ) 3. Hence, iodosylbenzene 1 is essentially insoluble in all nonreactive organic solvents 4,5…”

“…The linear O1‐I1‐O2 hypervalent bond of the aqua crown ether complex 6a is unsymmetrical, as observed in the polymeric structure of iodosylbenzene (Scheme ) 3. The hydroxy ligand in 6a is tightly bound to iodine(III), which is slightly shorter than that predicted (1.99 Å) for covalent radii, while the water ligand is loosely bound.…”

NMR study on the structure and stability of 4‐substituted aromatic iodosyl compounds

“…EXAFS (extended X-ray absorption fine structure) analysis has revealed that iodosylbenzene consists of a zigzag polymer structure in which monomeric Ph-IO units are linked by intermolecular non-symmetric I-O Ð Ð Ð I bridges. 6 Owing to the polymeric structure, iodosylbenzene is insoluble in all non-reactive solvents. The introduction of electronwithdrawing or donating substituents on the phenyl ring of iodosylbenzene changes the properties of the compound, influencing both the degree of association (R-Ph-IO) n and its reactivity as an oxidant.…”