Starting from the early 1990’s, the chemistry of polyvalent iodine organic compounds has experienced an explosive development. This surging interest in iodine compounds is mainly due to the very useful oxidizing properties of polyvalent organic iodine reagents, combined with their benign environmental character and commercial availability. Iodine(III) and iodine(V) derivatives are now routinely used in organic synthesis as reagents for various selective oxidative transformations of complex organic molecules. Several areas of hypervalent organoiodine chemistry have recently attracted especially active interest and research activity. These areas, in particular, include the synthetic applications of 2-iodoxybenzoic acid (IBX) and similar oxidizing reagents based on the iodine(V) derivatives, the development and synthetic use of polymer-supported and recyclable polyvalent iodine reagents, the catalytic applications of organoiodine compounds, and structural studies of complexes and supramolecular assemblies of polyvalent iodine compounds.

The chemistry of polyvalent iodine has previously been covered in four books1–4 and several comprehensive review papers.5–17 Numerous reviews on specific classes of polyvalent iodine compounds and their synthetic applications have recently been published.18–61 Most notable are the specialized reviews on [hydroxy(tosyloxy)iodo]benzene,41 the chemistry and synthetic applications of iodonium salts,29,36,38,42,43,46,47,54,55 the chemistry of iodonium ylides,56–58 the chemistry of iminoiodanes,28 hypervalent iodine fluorides,27 electrophilic perfluoroalkylations,44 perfluoroorgano hypervalent iodine compounds,61 the chemistry of benziodoxoles,24,45 polymer-supported hypervalent iodine reagents,30 hypervalent iodine-mediated ring contraction reactions,21 application of hypervalent iodine in the synthesis of heterocycles,25,40 application of hypervalent iodine in the oxidation of phenolic compounds,32,34,50–53,60 oxidation of carbonyl compounds with organohypervalent iodine reagents,37 application of hypervalent iodine in (hetero)biaryl coupling reactions,31 phosphorolytic reactivity of o-iodosylcarboxylates,33 coordination of hypervalent iodine,19 transition metal catalyzed reactions of hypervalent iodine compounds,18 radical reactions of hypervalent iodine,35,39 stereoselective reactions of hypervalent iodine electrophiles,48 catalytic applications of organoiodine compounds,20,49 and synthetic applications of pentavalent iodine reagents.22,23,26,59

The main purpose of the present review is to summarize the data that appeared in the literature following publication of our previous reviews in 1996 and 2002. In addition, a brief introductory discussion of the most important earlier works is provided in each section. The review is organized according to the classes of organic polyvalent iodine compounds with emphasis on their synthetic application. Literature coverage is through July 2008.

Chemistry of Polyvalent Iodine

Chemistry of iron sulfides.

About a century ago, researchers first recognized a connection between the activity of environmental microorganisms and cases of anaerobic iron corrosion. Since then, such microbially influenced corrosion (MIC) has gained prominence and its technical and economic implications are now widely recognized. Under anoxic conditions (e.g., in oil and gas pipelines), sulfate-reducing bacteria (SRB) are commonly considered the main culprits of MIC. This perception largely stems from three recurrent observations. First, anoxic sulfate-rich environments (e.g., anoxic seawater) are particularly corrosive. Second, SRB and their characteristic corrosion product iron sulfide are ubiquitously associated with anaerobic corrosion damage, and third, no other physiological group produces comparably severe corrosion damage in laboratory-grown pure cultures. However, there remain many open questions as to the underlying mechanisms and their relative contributions to corrosion. On the one hand, SRB damage iron constructions indirectly through a corrosive chemical agent, hydrogen sulfide, formed by the organisms as a dissimilatory product from sulfate reduction with organic compounds or hydrogen ("chemical microbially influenced corrosion"; CMIC). On the other hand, certain SRB can also attack iron via withdrawal of electrons ("electrical microbially influenced corrosion"; EMIC), viz., directly by metabolic coupling. Corrosion of iron by SRB is typically associated with the formation of iron sulfides (FeS) which, paradoxically, may reduce corrosion in some cases while they increase it in others. This brief review traces the historical twists in the perception of SRB-induced corrosion, considering the presently most plausible explanations as well as possible early misconceptions in the understanding of severe corrosion in anoxic, sulfate-rich environments.

Corrosion of Iron by Sulfate-Reducing Bacteria: New Views of an Old Problem

Acid volatile sulfide (AVS)

Bismuth compounds and preparations with biological or medicinal relevance.

A review of the oxidation of uranium dioxide at temperatures below 400°C

The initial stages of corrosion of iron by unstirred saturated aqueous H/sub 2/S solutions at 21/sup 0/C and atmospheric pressure have been examined as a function of time, pH (from 2 to 7, adjusted by addition of H/sub 2/SO/sub 4/ or NaOH), and applied current. Detailed examination of the morphology and phase identity of the corrosion products has led to a qualitative mechanistic understanding of the corrosion reactions. Mackinawite (tetragonal FeS/sub 1-x/) is formed by both solid-state and precipitation processes. Cubic ferrous sulfide and troilite occur as precipitates between pH = 3 and pH = 5, subsequent to metal dissolution upon cracking of a mackinawite base layer formed by a solid-state mechanism. The corrosion rate, and the relative amounts of these phases produced, are controlled by pH, applied current, and the degree of convection. The corrosion rate increases with decreasing pH; the quantity of precipitated material peaks near pH = 4, below which dissolution becomes the dominant process as the solubilities of the sulfide solids increase. Significant passivation was observed only at pH = 7, when the initial mackinawite base layer remained virtually intact. The solid-state conversion of cubic ferrous sulfide to mackinawite at 21/sup 0/C was monitored by x-raymore » diffractometry. The resulting kinetics are consistent with the Avrami equation for a nucleation and growth process with a time exponent of 3.« less

https://iopscience.iop.org/article/10.1149/1.2129808/pdf

The Formation of Ferrous Monosulfide Polymorphs during the Corrosion of Iron by Aqueous Hydrogen Sulfide at 21°C

Identification du carbonate (BiO) 4 (OH) 2 CO 3 comme intermediaire dans l'interconversion de α-Bi 2 O 3 et de la bismutite synthetique (BiO) 2 CO 3 . Energies de formation de Gibbs, analyse thermogravimetrique, diffraction RX sur poudre et spectrometries IR et Raman. Parametres cristallins

Structure, spectra, and stability of solid bismuth carbonates

Four basic lead carbonates were prepared and identified by X-ray powder diffractometry. These were hydrocerussite (Pb3(OH)2(CO3)2), plumbonacrite (Pb10O(OH)6(CO3)6), and the two adducts MOH•2PbCO3 ...

Peter Taylor

Papers

A review of the oxidation of uranium dioxide at temperatures below 400°C

The Formation of Ferrous Monosulfide Polymorphs during the Corrosion of Iron by Aqueous Hydrogen Sulfide at 21°C

Structure, spectra, and stability of solid bismuth carbonates

Infrared and Raman spectra and X-ray diffraction studies of solid lead(II) carbonates

Electrochemical behaviour of iron in alkaline sulphide solutions