Iodosobenzene

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Iodosobenzene
PhIO-from-PXRD-0-double-chain-view-3-Mercury-3D-bs.png
Names
Preferred IUPAC name
Iodosylbenzene [1]
Other names
Iodosobenzene
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.007.864 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 208-648-8
PubChem CID
UNII
  • InChI=1S/C6H5IO/c8-7-6-4-2-1-3-5-6/h1-5H Yes check.svgY
    Key: JYJVVHFRSFVEJM-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C6H5IO/c8-7-6-4-2-1-3-5-6/h1-5H
    Key: JYJVVHFRSFVEJM-UHFFFAOYAR
  • c1ccc(cc1)I=O
Properties
C6H5IO
Molar mass 220.01 g/mol
Appearancecolourless solid
Density 1.229 g cm−3
Melting point 210 ˚C
poor
Hazards
GHS labelling: [2]
GHS-pictogram-flamme.svg GHS-pictogram-rondflam.svg GHS-pictogram-exclam.svg
Danger
H228, H271, H315, H319, H335
P210, P220, P240, P241, P261, P264, P264+P265, P271, P280, P283, P302+P352, P304+P340, P305+P351+P338, P306+P360, P319, P321, P332+P317, P337+P317, P362+P364, P370+P378, P371+P380+P375, P403+P233, P405, P420, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Iodosobenzene or iodosylbenzene is an organoiodine compound with the empirical formula C6H5IO. This colourless solid compound is used as an oxo transfer reagent in research laboratories examining organic and coordination chemistry.

Contents

Preparation and structure

Iodosobenzene is prepared from iodobenzene. [3] It is prepared by first oxidizing iodobenzene by peracetic acid. Hydrolysis of resulting diacetate affords "PhIO": [4]

C6H5I + CH3CO3H + CH3CO2H → C6H5I(O2CCH3)2 + H2O
C6H5I(O2CCH3)2 + H2O → C6H5IO + 2 CH3CO2H

The structure of iodosobenzene has been verified by crystallographically. [5] Related derivatives are also oligomeric. [6] 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. [7] The related diacetate, C6H5I(O2CCH3)2, illustrates the ability of iodine(III) to adopt a T-shaped geometry without multiple bonds. [8] 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. [9]

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. [10]

Structure of 2-(tert-butylsulfonyl)iodosylbenzene. 2-(tert-butylsulfonyl)iodosylbenzene (MEHKUF).png
Structure of 2-(tert-butylsulfonyl)iodosylbenzene.

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. [11]

A mixture of iodosobenzene and sodium azide in acetic acid converts alkenes to vicinal diazides:. [12] [13]

R2C=CR2 + 2 NaN3 + PhIO + 2 AcOH → (N3)R2C−CR2(N3) + PhI + 2 AcONa + H2O

Safety

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

See also

Related Research Articles

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<span class="mw-page-title-main">Imine</span> Organic compound or functional group containing a C=N bond

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<span class="mw-page-title-main">(Bis(trifluoroacetoxy)iodo)benzene</span> Chemical compound

(Bis iodo)benzene, C
6
H
5
I(OCOCF
3
)
2
, is a hypervalent iodine compound used as a reagent in organic chemistry. It can be used to carry out the Hofmann rearrangement under acidic conditions.

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<span class="mw-page-title-main">Trifluoroperacetic acid</span> Chemical compound

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3
COOOH
. It is a strong oxidizing agent for organic oxidation reactions, such as in Baeyer–Villiger oxidations of ketones. It is the most reactive of the organic peroxy acids, allowing it to successfully oxidise relatively unreactive alkenes to epoxides where other peroxy acids are ineffective. It can also oxidise the chalcogens in some functional groups, such as by transforming selenoethers to selones. It is a potentially explosive material and is not commercially available, but it can be quickly prepared as needed. Its use as a laboratory reagent was pioneered and developed by William D. Emmons.

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6
H
5
I(OCOCH
3
)
2
. It is used as an oxidizing agent in organic chemistry.

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References

  1. International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 661. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  2. "Iodosylbenzene". pubchem.ncbi.nlm.nih.gov.
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  12. Robert M.Moriarty; Jaffar S.Khosrowshahi (1986). "A versatile synthesis of vicinal diazides using hypervalent iodine". Tetrahedron Lett. 27 (25): 2809–2812. doi:10.1016/S0040-4039(00)84648-1.
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