Iodosobenzene

Preparation and structure

Iodosobenzene is prepared from iodobenzene. It is prepared by first oxidizing iodobenzene by peracetic acid. Hydrolysis of resulting diacetate affords "PhIO":

: :

The structure of iodosobenzene has been verified by crystallographically. Related derivatives are also oligomeric. Its low solubility in most solvents and vibrational spectroscopy indicate that it is not molecular, but is polymeric, consisting of –I–O–I–O– chains. The related diacetate, , illustrates the ability of iodine(III) to adopt a T-shaped geometry without multiple bonds. Theoretical studies show that the bonding between the iodine and oxygen atoms in iodosobenzene represents a single dative I-O sigma bond, confirming the absence of the double I=O bond.

A monomeric derivative iodosylbenzene is known in the form of 2-(tert-butylsulfonyl)iodosylbenzene, a yellow solid. C-I-O angle is 94.78°, C-I and I-O distances are 2.128 and 1.848 Å.

Applications

Iodosobenzene has no commercial uses, but in the laboratory it is employed as an "oxo-transfer reagent." It epoxidizes certain alkenes and converts some metal complexes into the corresponding oxo derivatives. Although it is an oxidant, it is also mildly nucleophilic. These oxo-transfer reactions operate by the intermediacy of adducts PhI=O→M, which release PhI.

A mixture of iodosobenzene and sodium azide in acetic acid converts alkenes to vicinal diazides:.

:

Safety

This compound is explosive and should not be heated under vacuum.

References

References

1. [[International Union of Pure and Applied Chemistry]]. (2014). "Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013". [[Royal Society of Chemistry.
2. "Iodosylbenzene".
3. Conrad Willgerodt. (1892). "Zur Kenntniss aromatischer Jodidchloride, des Jodoso- und Jodobenzols". [[Chemische Berichte.
4. H. Saltzman, J. G. Sharefkin. (1963). "Iodosylbenzene". Organic Syntheses.
5. (2016). "Reduction of hypervalent iodine by coordination to iron(III) and the crystal structures of PhIO and PhIO2". Dalton Transactions.
6. (2007). "Preparation and Structure of a Solid-State Hypervalent-Iodine Polymer Containing Iodine and Oxygen Atoms in Fused 12-Atom Hexagonal Rings". Inorganic Chemistry.
7. (1976). "Schwingungsspektren und Struktur von Jodosyl- und Jodyl-Verbindungen". [[Zeitschrift für anorganische und allgemeine Chemie.
8. (1994). "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". [[Chemical Communications.
9. Ivanov, A.. (2014). "The I=X (X = O,N,C) Double Bond in Hypervalent Iodine Compounds: Is it Real?". Angew. Chem. Int. Ed..
10. (2000). "Redirecting Secondary Bonds to Control Molecular and Crystal Properties of an Iodosyl- and an Iodylbenzene". Angewandte Chemie International Edition.
11. (2012). "An Iron(III) Iodosylbenzene Complex: A Masked Non-Heme FeVO". Angewandte Chemie International Edition.
12. Robert M.Moriarty. (1986). "A versatile synthesis of vicinal diazides using hypervalent iodine". [[Tetrahedron Letters.
13. (2007). "Advanced Organic Chemistry". John Wiley & Sons.