Organoastatine chemistry

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Organoastatine chemistry describes the synthesis and properties of organoastatine compounds, chemical compounds containing a carbon to astatine chemical bond.

Astatine is extremely radioactive, with the longest-lived isotope (210At) having a half-life of only 8.1 hours. Consequently, organoastatine chemistry can only be studied by tracer techniques on extremely small quantities. The problems caused by radiation damage as well as difficulties in separation and identification are worse for organic astatine derivatives than for inorganic compounds. Most studies of organoastatine chemistry focus on 211At (half-life 7.21 hours), which is the subject of ongoing studies in nuclear medicine: it is better than 131I at destroying abnormal thyroid tissue. [1]

Astatine-labelled iodine reagents have been used to synthesise RAt, RAtCl2, R2AtCl, and RAtO2 (R = phenyl or p-tolyl). [1] Alkyl and aryl astatides are relatively stable and have been analysed at high temperatures (120 °C) with radio gas chromatography. [2] Demercuration reactions have produced with good yields trace quantities of 211At-containing aromatic amino acids, steroids, and imidazols, among other compounds. [1]

Astatine has both halogen-like and metallic properties, so that analogies with iodine sometimes hold, but sometimes do not. Astatine can be incorporated into organic molecules via halogen exchange, halodediazotation (replacing a diazonium group), halodeprotonation, or halodemetallation. Initial attempts to radiolabel proteins with 211At exemplify its intermediate behaviour, as astatination (analogous to radioiodination) produces unstable results and it is instead AtO+ (or a hydrolysed species) that probably bonds to proteins. Two-step procedures are used today, first synthesising stable astatoaryl prosthetic groups before incorporating them into the protein. [3] Not only is the C–At bond the weakest of all carbon–halogen bonds (following periodic trends), but also the bond easily breaks as the astatine is oxidised back to free astatine. [3]

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<span class="mw-page-title-main">Astatine</span> Chemical element, symbol At and atomic number 85

Astatine is a chemical element with the symbol At and atomic number 85. It is the rarest naturally occurring element in the Earth's crust, occurring only as the decay product of various heavier elements. All of astatine's isotopes are short-lived; the most stable is astatine-210, with a half-life of 8.1 hours. A sample of the pure element has never been assembled, because any macroscopic specimen would be immediately vaporized by the heat of its radioactivity.

<span class="mw-page-title-main">Bromine</span> Chemical element, symbol Br and atomic number 35

Bromine is a chemical element with the symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig and Antoine Jérôme Balard, its name was derived from the Ancient Greek βρῶμος (bromos) meaning "stench", referring to its sharp and pungent smell.

<span class="mw-page-title-main">Halogen</span> Group of chemical elements

The halogens are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and tennessine (Ts), though some authors would exclude tennessine as its chemistry is unknown and is theoretically expected to be more like that of gallium. In the modern IUPAC nomenclature, this group is known as group 17.

<span class="mw-page-title-main">Iodine</span> Chemical element, symbol I and atomic number 53

Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at 114 °C (237 °F), and boils to a violet gas at 184 °C (363 °F). The element was discovered by the French chemist Bernard Courtois in 1811 and was named two years later by Joseph Louis Gay-Lussac, after the Ancient Greek Ιώδης 'violet-coloured'.

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

<span class="mw-page-title-main">Catenation</span> Bonding of atoms of the same element into chains or rings

In chemistry, catenation is the bonding of atoms of the same element into a series, called a chain. A chain or a ring shape may be open if its ends are not bonded to each other, or closed if they are bonded in a ring. The words to catenate and catenation reflect the Latin root catena, "chain".

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens (F2, Cl2, Br2, I2). Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

Halocarbon compounds are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms resulting in the formation of organofluorine compounds, organochlorine compounds, organobromine compounds, and organoiodine compounds. Chlorine halocarbons are the most common and are called organochlorides.

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

In chemistry, a non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The chemical energy released in the formation of non-covalent interactions is typically on the order of 1–5 kcal/mol. Non-covalent interactions can be classified into different categories, such as electrostatic, π-effects, van der Waals forces, and hydrophobic effects.

<span class="mw-page-title-main">Halonium ion</span> Any onium ion containing a halogen atom carrying a positive charge

A halonium ion is any onium ion containing a halogen atom carrying a positive charge. This cation has the general structure R−+X−R′ where X is any halogen and no restrictions on R, this structure can be cyclic or an open chain molecular structure. Halonium ions formed from fluorine, chlorine, bromine, and iodine are called fluoronium, chloronium, bromonium, and iodonium, respectively. The 3-membered cyclic variety commonly proposed as intermediates in electrophilic halogenation may be called haliranium ions, using the Hantzsch-Widman nomenclature system.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.

A cyanogen halide is a molecule consisting of cyanide and a halogen. Cyanogen halides are chemically classified as pseudohalogens.

A halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. Like a hydrogen bond, the result is not a formal chemical bond, but rather a strong electrostatic attraction. Mathematically, the interaction can be decomposed in two terms: one describing an electrostatic, orbital-mixing charge-transfer and another describing electron-cloud dispersion. Halogen bonds find application in supramolecular chemistry; drug design and biochemistry; crystal engineering and liquid crystals; and organic catalysis.

Organoiodine chemistry is the study of the synthesis and properties of organoiodine compounds, or organoiodides, organic compounds that contain one or more carbon–iodine bonds. They occur widely in organic chemistry, but are relatively rare in nature. The thyroxine hormones are organoiodine compounds that are required for health and the reason for government-mandated iodization of salt.

Iodane generally refers to any organic derivative of iodine. Without modifier, iodane is the systematic name for the parent hydride of iodine, HI. Thus, any organoiodine compound with general formula RI is a substituted iodane. However, as used in the context of organic synthesis, the term iodane more specifically refers to organoiodine compounds with nonstandard bond order of bonds between iodine and other atoms, i.e., bond order of iodine greater than 1, making this term a synonym for hypervalent iodine. These iodine compounds are hypervalent because the iodine atom formally contains more than the 8 electrons in the valence shell required for the octet rule. When iodine is ligated to an organic residue and electronegative ligands, hypervalent iodine occurs in a +3 oxidation state as iodine(III) or λ3-iodane, or in a +5 oxidation state as iodine(V) or λ5-iodane, or in a +7 oxidation state as iodine(VII) or λ7-iodane. Here, lambda convention is used to give the nonstandard bond order.

In organic chemistry, dehalogenation is a set of chemical reactions that involve the cleavage of carbon-halogen bonds; as such, it is the inverse reaction of halogenation. Dehalogenations come in many varieties, including defluorination, dechlorination, debromination, and deiodination. Incentives to investigate dehalogenations include both constructive and destructive goals. Complicated organic compounds such as pharmaceutical drugs are occasionally generated by dehalogenation. Many organohalides are hazardous, so their dehalogenation is one route for their detoxification.

Fluorine forms a great variety of chemical compounds, within which it always adopts an oxidation state of −1. With other atoms, fluorine forms either polar covalent bonds or ionic bonds. Most frequently, covalent bonds involving fluorine atoms are single bonds, although at least two examples of a higher order bond exist. Fluoride may act as a bridging ligand between two metals in some complex molecules. Molecules containing fluorine may also exhibit hydrogen bonding. Fluorine's chemistry includes inorganic compounds formed with hydrogen, metals, nonmetals, and even noble gases; as well as a diverse set of organic compounds. For many elements the highest known oxidation state can be achieved in a fluoride. For some elements this is achieved exclusively in a fluoride, for others exclusively in an oxide; and for still others the highest oxidation states of oxides and fluorides are always equal.

<span class="mw-page-title-main">Astatine compounds</span>

Astatine compounds are compounds that contain the element astatine (At). As this element is very radioactive, few compounds have been studied. Less reactive than iodine, astatine is the least reactive of the halogens. Its compounds have been synthesized in nano-scale amounts and studied as intensively as possible before their radioactive disintegration. The reactions involved have been typically tested with dilute solutions of astatine mixed with larger amounts of iodine. Acting as a carrier, the iodine ensures there is sufficient material for laboratory techniques to work. Like iodine, astatine has been shown to adopt odd-numbered oxidation states ranging from −1 to +7.

References

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  2. Coenen, H. H.; Moerlein, S. M.; Stöcklin, G. (1983). "No-Carrier-Added Radiohalogenation Methods with Heavy Halogens". Radiochimica Acta. 34 (1–2): 47–68. doi:10.1524/ract.1983.34.12.47. S2CID   99845370.
  3. 1 2 Guérard, François; Maingueneau, Clémence; Liu, Lu; Eychenne, Romain; Gestin, Jean-François; Montavon, Gilles; Galland, Nicolas (2021). "Advances in the Chemistry of Astatine and Implications for the Development of Radiopharmaceuticals" (PDF). Accounts of Chemical Research. 54 (16): 3264–3275. doi:10.1021/acs.accounts.1c00327. PMID   34350753. S2CID   236926712.

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