Preparation and Structure of Oligomeric Iodosylbenzene Sulfate (PhIO)₃·SO₃: Stable and Water‐Soluble Analog of Iodosylbenzene

Abstract

New phenyliodine(III) sulfate (PhIO)3·SO3, which has a complex polymeric structure of the trimeric iodosylbenzene units linked by sulfate anions, can be conveniently prepared by treatment of (diacetoxy)iodobenzene with sodium bisulfate in the presence of water. This sulfate can find practical application as a readily available, stable, and water‐soluble hypervalent iodine reagent with a reactivity pattern similar tothat of iodosylbenzene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Chemistry of Polyvalent Iodine

“…In particular, iodine atoms in the (PhIO) 3 fragment of the oligomeric sulfate 8 exhibit a typical of trivalent iodine T-shaped intramolecular geometry with O-I-O and O-I-C bond angles close to 180° (166.54–177.99) and 90° (79.18–92.43), respectively. The I-O bond distances in the (PhIO) 3 fragment of sulfate 8 vary in a broad range of 1.95 to 2.42 Å 121. The single crystal X-ray crystal study of the oligomeric perchlorate 9 revealed a complex structure consisting of pentaiodanyl dicationic units joined by secondary I•••O bonds into an infinite linear structure of 12-atom hexagonal rings 87.…”

A Simple and Highly Selective Biomimetic Oxidation of Alcohols with Hypervalent Iodine(III) Reagent Catalyzed by β-Cyclodextrin in Water

“…First, a range of hypervalent iodine reagents such as PhI(OAc) 2 , PhI (OH)OTs, PhIO 2 , PhICl 2 , PhI(OCOCF 3 ) 2 , and PhIO were used as oxidant in the reaction, however, all of them were not satisfactory probably due to their poor solubility in water ( Table 1, entries 1-6). Recently, Zhdankin and co-workers [35,36] have reported a mild and efficient method for the preparation of oligomeric iodosylbenzene sulfate (PhIO) 3 ÁSO 3 . This sulfate can find practical application as a readily available, stable, and water-soluble hypervalent iodine reagent with a reactivity pattern similar to iodosylbenzene [37,38].…”

“…GC-MS spectra were recorded on Thermo Trace DSQ GC-MS spectrometer using TRB-5MS (30 m 9 0.25 mm 9 0.25 lm) column. (PhIO) 3 ÁSO 3 was prepared from commercially available PhI(OAc) 2 and NaHSO 4 ÁH 2 O by a procedure described in the literature [35,36]. Other reagents (AR grade) were obtained from commercial resources and used without further purification.…”

Comparative Reactivity of Hypervalent Iodine Oxidants in Metalloporphyrin‐Catalyzed Oxygenation of Hydrocarbons: Iodosylbenzene Sulfate and 2‐Iodylbenzoic Acid Ester as Safe and Convenient Alternatives to Iodosylbenzene

“…[4] In this communication, we report preliminary results on the use of the new and convenient hypervalent iodine reagents 1 and 2 ( Figure 1) as terminal oxidants in the biomimetic oxidation of anthracene to anthraquinone catalyzed by FeA C H T U N G T R E N N U N G (III) phthalocyanine complex 3 (Figure 2), Co(II) tetraphenylporphyrin (4) or Ru(II) tetraphenylporphyrin (5).…”

“…[5] The isopropyl ester of 2-iodylbenzoic acid (IBX-ester) (1) was prepared by the hypochlorite oxidation of the readily available isopropyl ester of 2-iodobenzoic acid and isolated in the form of a stable, white, microcrystalline solid. [6a,b] Reagent 1 is also commercially available from several chemical companies.…”