The water–iodine oxide system: a revised mechanism for hydration and dehydration

Smith, Douglas A.; Pantoya, Michelle L.; Parkey, Jeffrey S.; Kesmez, Mehmet

doi:10.1039/c6ra27854j

Cited by 14 publications

(13 citation statements)

References 13 publications

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“…Because of this direct dehydration into I 2 O 5 during slow heating, δ-HIO 3 is reported as metastable. This can be explained by the metastable nature of β-HIO 3 reported here and results from Smith et al [18] showing that HIO 3 dehydrates directly into I 2 O 5 and HI 3 O 8 is formed during heating. Since comparison between measurements in Halasz et al [8] and diffraction patterns obtained, using modern XRD are difficult to quantify, it is probable that δ-HIO 3 identified by Wu et al [9] is actually β-HIO 3 .…”

Section: Discussionsupporting

confidence: 71%

Discovery of β-HIO3: A Metastable Polymorph of HIO3

Smith¹,

Unruh²,

Pantoya³

2018

AMPC

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The β-HIO 3 polymorph, previously difficult to detect and whose existence was questioned, has been structurally characterized. The crystal structure of β-HIO 3 was solved in the same space group as α-HIO 3 (P212121); however, it was found that the unit cell axes were all different by about 1 Å. Similar to that of α and γ phases, the unit cell contains only a single HIO 3 molecule in the asymmetric unit with I-O bond lengths ranging from 1.786(5) to 1.903(7) Å. The I(V) atom is further coordinated by three oxygen atoms of neighboring acid molecules forming a distorted octahedral with a range of I-O distances (2.498(6)-2.795(7) Å). The one structural difference that separates the β phase from the α and γ phases is that the hydroxyl group is bridging between two I(V) atoms, resulting in a smaller hydrogen bonding distance (O-O distance: 2.559 Å (β), 2.665 Å (γ) and 2.696 Å (α)) and presumably a different crystalline energy. Similar to γ-HIO 3 , β-HIO 3 is metastable and slowly converts to α-HIO 3. It is hypothesized that β-HIO 3 is a transition step in the formation of α-HIO 3 and β-HIO 3 is a result of trapped water inside particles during crystallization.

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Section: Discussionsupporting

confidence: 71%

Discovery of β-HIO3: A Metastable Polymorph of HIO3

Smith¹,

Unruh²,

Pantoya³

2018

AMPC

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“…20,[39][40] For iodine pentoxide-iodic acid hybrid clusters, the sorption of water vapor is of particular interest, as water facilitates the interconversion of iodine pentoxide and iodic acid. [41][42] We examined water vapor sorption at 295 K and saturation ratios from 0.0 to 0.65 through monitoring CCS shifts for the cluster ions (HIO 3 )IO 3and (I 2 O 5 ) x IO 3 -(x = 1 -7). Figure 3a displays plot of the CCS as a function of saturation ratio.…”

mentioning

confidence: 99%

Ion Mobility-Mass Spectrometry of Iodine Pentoxide–Iodic Acid Hybrid Cluster Anions in Dry and Humidified Atmospheres

Ahonen

Kubečka

et al. 2019

J. Phys. Chem. Lett.

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Nanometer scale clusters form from vapor phase precursors and can subsequently grow into nanoparticles during atmospheric nucleation events. A particularly interesting set of clusters relevant to nucleation is hybrid iodine pentoxide-iodic acid clusters of the form (I 2 O 5) x (HIO 3) y , as these clusters have been observed in coastal region nucleation events in anomalously high concentrations. To better understand their properties, we have utilized ion mobility-mass spectrometry to probe the structures of cluster anions of the form (I 2 O 5) x (HIO 3) y (IO α)-(x = 0-7, y = 0-1, α = 1-3), similar to those observed in coastal nucleation events. We show that (I 2 O 5) x (HIO 3) y (IO α)clusters are relatively stable against dissociation during mass spectrometric measurement, as compared to other clusters observed in nucleation events over continental sites, and that at atmospherically relevant relative humidity levels (65% and less), clusters can become sufficiently hydrated to facilitate complete conversion of iodine pentoxide to iodic acid, but that water sorption beyond this level is limited, indicating that the clusters do not persist as nanometer scale droplets in the ambient.

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“…However, it is still necessary to verify the potential electrophilic species and iodine sources in our reaction system. It is well known that I 2 O 5 can hydrate into iodic acid (HIO 3 ). , However, when commercially available HIO 3 was employed, none of the desired product was detected (Scheme , eq 2). In addition, no product was obtained in the absence of LiI (Table , entry 14).…”

Section: Results and Discussionmentioning

confidence: 99%

Environmentally Friendly Protocol for the Oxidative Iodofunctionalization of Olefins in a Green Solvent

Wang

et al. 2019

ACS Sustainable Chem. Eng.

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An environmentally friendly iodofunctionalization of olefins for the synthesis of various iodinated products was developed via the oxidative umpolung of iodide using I 2 O 5 as the inorganic oxidant. The distinct advantages of this protocol over all previous methods include no generation of organic byproducts and the use of a green solvent, thus greatly reducing the environmental impact. Additionally, mild reaction conditions, good yields, and easy-to-operate features make the current reaction system a more attractive method for the synthesis of a variety of medicinal and agrochemical compounds of interest.

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The water–iodine oxide system: a revised mechanism for hydration and dehydration

Abstract: Iodic acids are widely studied in atmospheric and biological applications but their inherent hydrophilic properties introduce complexities that affect their functionality and reactivity.

Cited by 14 publications

References 13 publications

Discovery of <i>β</i>-HIO<sub>3</sub>: A Metastable Polymorph of HIO<sub>3</sub>

Discovery of <i>β</i>-HIO<sub>3</sub>: A Metastable Polymorph of HIO<sub>3</sub>

Ion Mobility-Mass Spectrometry of Iodine Pentoxide–Iodic Acid Hybrid Cluster Anions in Dry and Humidified Atmospheres

Environmentally Friendly Protocol for the Oxidative Iodofunctionalization of Olefins in a Green Solvent

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The water–iodine oxide system: a revised mechanism for hydration and dehydration

Abstract: Iodic acids are widely studied in atmospheric and biological applications but their inherent hydrophilic properties introduce complexities that affect their functionality and reactivity.

Cited by 14 publications

References 13 publications

Discovery of &lt;i&gt;β&lt;/i&gt;-HIO&lt;sub&gt;3&lt;/sub&gt;: A Metastable Polymorph of HIO&lt;sub&gt;3&lt;/sub&gt;

Discovery of &lt;i&gt;β&lt;/i&gt;-HIO&lt;sub&gt;3&lt;/sub&gt;: A Metastable Polymorph of HIO&lt;sub&gt;3&lt;/sub&gt;

Ion Mobility-Mass Spectrometry of Iodine Pentoxide–Iodic Acid Hybrid Cluster Anions in Dry and Humidified Atmospheres

Environmentally Friendly Protocol for the Oxidative Iodofunctionalization of Olefins in a Green Solvent

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Discovery of <i>β</i>-HIO<sub>3</sub>: A Metastable Polymorph of HIO<sub>3</sub>

Discovery of <i>β</i>-HIO<sub>3</sub>: A Metastable Polymorph of HIO<sub>3</sub>