Cation–cation bond

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Cation-cation interactions often occur between molecular cations of transition metals and f-elements (so-called yl cations). They are distinguished as a separate type of intermolecular interactions, since without taking them into account, cations usually repel each other in accordance with Coulomb's law.

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Cation-cation interactions in f-elements

Of particular interest are cation-cation interactions between actinide cations - uranium, in the form of uranyl UO22+, neptunium in the form of neptunoyl NpO22+, plutonium and americium, which are essentially a manifestation of specific complex formation. [1] They are a special case of intermolecular interactions that occur in molecular ions. It was first discovered when studying the behavior of netunium(V) compounds in solutions of uranyl perchlorate. [2] Great impact to crystallochemistry of cation-cation bonds was made by Mikhail Grigoriev.

The cation-cation interaction [NpO2]+ determines the crystal structure of Np(V) compounds, and the strength of cation-cation bonds between neptunoyl ions in a solid is comparable to the strength of ordinary bonds with acid ligands, [3] although in an aqueous solution, apparently, the role There are somewhat fewer of these connections. In an organic solution, the intensity of C-C interactions can remain high [1]. In the absence of mutual coordination of neptunium ions, Np(V) compounds can exhibit both structural similarity with An(VI) compounds and fundamental differences (showing a tendency to unite Np coordination polyhedra through common equatorial edges. Cation-cation interactions can be detected not only by data from structural studies, but also according to vibrational spectroscopy data. [4] For uranyl, cation-cation interactions are also recorded in the gas phase. [5]

Cation-cation interactions in transition metal ions

For transition metals, cation-cation interactions appear in nitrene complexes. [6] Nitrenium ligands provide an excellent platform for the simple and efficient synthesis of extremely rare complexes that have positively charged ligands coordinated to positively charged metals to form stable cation-cation and cation-dication coordination bonds.[ citation needed ]

Related Research Articles

The actinide or actinoid series encompasses at least the 14 metallic chemical elements in the 5f series, with atomic numbers from 89 to 102, actinium through nobelium. The actinide series derives its name from the first element in the series, actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide.

<span class="mw-page-title-main">Coordination complex</span> Molecule or ion containing ligands datively bonded to a central metallic atom

A coordination complex is a chemical compound consisting of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those that include transition metals, are coordination complexes.

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

<span class="mw-page-title-main">Neptunium</span> Chemical element, symbol Np and atomic number 93

Neptunium is a chemical element; it has symbol Np and atomic number 93. A radioactive actinide metal, neptunium is the first transuranic element. Its position in the periodic table just after uranium, named after the planet Uranus, led to it being named after Neptune, the next planet beyond Uranus. A neptunium atom has 93 protons and 93 electrons, of which seven are valence electrons. Neptunium metal is silvery and tarnishes when exposed to air. The element occurs in three allotropic forms and it normally exhibits five oxidation states, ranging from +3 to +7. Like all actinides, it is radioactive, poisonous, pyrophoric, and capable of accumulating in bones, which makes the handling of neptunium dangerous.

<span class="mw-page-title-main">Polyoxometalate</span> Polyatomic ion made of ≥3 transition metal oxyanions bound by oxygen in a 3D structure

In chemistry, a polyoxometalate is a polyatomic ion, usually an anion, that consists of three or more transition metal oxyanions linked together by shared oxygen atoms to form closed 3-dimensional frameworks. The metal atoms are usually group 6 or less commonly group 5 and group 7 transition metals in their high oxidation states. Polyoxometalates are often colorless, orange or red diamagnetic anions. Two broad families are recognized, isopolymetalates, composed of only one kind of metal and oxide, and heteropolymetalates, composed of one metal, oxide, and a main group oxyanion. Many exceptions to these general statements exist.

<span class="mw-page-title-main">Uranyl</span> Oxycation of uranium

The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula UO2+
2
. It has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen. Four or more ligands may be bound to the uranyl ion in an equatorial plane around the uranium atom. The uranyl ion forms many complexes, particularly with ligands that have oxygen donor atoms. Complexes of the uranyl ion are important in the extraction of uranium from its ores and in nuclear fuel reprocessing.

<span class="mw-page-title-main">Uranium trioxide</span> Chemical compound

Uranium trioxide (UO3), also called uranyl oxide, uranium(VI) oxide, and uranic oxide, is the hexavalent oxide of uranium. The solid may be obtained by heating uranyl nitrate to 400 °C. Its most commonly encountered polymorph, γ-UO3, is a yellow-orange powder.

Uranyl sulfate describes a family of inorganic compounds with the formula UO2SO4(H2O)n. These salts consist of sulfate, the uranyl ion, and water. They are lemon-yellow solids. Uranyl sulfates are intermediates in some extraction methods used for uranium ores. These compounds can also take the form of an anhydrous salt.

<span class="mw-page-title-main">Coordination sphere</span> All ligands directly bound to the central metal atom of a chemical complex

In coordination chemistry, the first coordination sphere refers to the array of molecules and ions directly attached to the central metal atom. The second coordination sphere consists of molecules and ions that attached in various ways to the first coordination sphere.

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

Vanadium compounds are compounds formed by the element vanadium (V). The chemistry of vanadium is noteworthy for the accessibility of the four adjacent oxidation states 2–5, whereas the chemistry of the other group 5 elements, niobium and tantalum, are somewhat more limited to the +5 oxidation state. In aqueous solution, vanadium forms metal aquo complexes of which the colours are lilac [V(H2O)6]2+, green [V(H2O)6]3+, blue [VO(H2O)5]2+, yellow-orange oxides [VO(H2O)5]3+, the formula for which depends on pH. Vanadium(II) compounds are reducing agents, and vanadium(V) compounds are oxidizing agents. Vanadium(IV) compounds often exist as vanadyl derivatives, which contain the VO2+ center.

<span class="mw-page-title-main">Organoactinide chemistry</span> Study of chemical compounds containing actinide-carbon bonds

Organoactinide chemistry is the science exploring the properties, structure, and reactivity of organoactinide compounds, which are organometallic compounds containing a carbon to actinide chemical bond.

In coordination chemistry, a stability constant is an equilibrium constant for the formation of a complex in solution. It is a measure of the strength of the interaction between the reagents that come together to form the complex. There are two main kinds of complex: compounds formed by the interaction of a metal ion with a ligand and supramolecular complexes, such as host–guest complexes and complexes of anions. The stability constant(s) provide(s) the information required to calculate the concentration(s) of the complex(es) in solution. There are many areas of application in chemistry, biology and medicine.

Zinc compounds are chemical compounds containing the element zinc which is a member of the group 12 of the periodic table. The oxidation state of zinc in most compounds is the group oxidation state of +2. Zinc may be classified as a post-transition main group element with zinc(II). Zinc compounds are noteworthy for their nondescript appearance and behavior: they are generally colorless, do not readily engage in redox reactions, and generally adopt symmetrical structures.

Organogold chemistry is the study of compounds containing gold–carbon bonds. They are studied in academic research, but have not received widespread use otherwise. The dominant oxidation states for organogold compounds are I with coordination number 2 and a linear molecular geometry and III with CN = 4 and a square planar molecular geometry.

The plutonyl ion is an oxycation of plutonium in the oxidation state +6, with the chemical formula PuO2+
2
. It is isostructural with the uranyl ion, compared to which it has a slightly shorter M–O bond. It is easily reduced to plutonium(III). The plutonyl ion forms many complexes, particularly with ligands that have oxygen donor atoms. Complexes of the plutonyl ion are important in nuclear fuel reprocessing.

In chemistry, metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlorates. They have the general stoichiometry [M(H2O)n]z+. Their behavior underpins many aspects of environmental, biological, and industrial chemistry. This article focuses on complexes where water is the only ligand, but of course many complexes are known to consist of a mix of aquo and other ligands.

In chemistry, molecular oxohalides (oxyhalides) are a group of chemical compounds in which both oxygen and halogen atoms are attached to another chemical element A in a single molecule. They have the general formula AOmXn, where X is a halogen. Known oxohalides have fluorine (F), chlorine (Cl), bromine (Br), and/or iodine (I) in their molecules. The element A may be a main group element, a transition element, a rare earth element or an actinide. The term oxohalide, or oxyhalide, may also refer to minerals and other crystalline substances with the same overall chemical formula, but having an ionic structure.

<span class="mw-page-title-main">Thorium compounds</span> Any chemical compound having at least one atom of thorium

Many compounds of thorium are known: this is because thorium and uranium are the most stable and accessible actinides and are the only actinides that can be studied safely and legally in bulk in a normal laboratory. As such, they have the best-known chemistry of the actinides, along with that of plutonium, as the self-heating and radiation from them is not enough to cause radiolysis of chemical bonds as it is for the other actinides. While the later actinides from americium onwards are predominantly trivalent and behave more similarly to the corresponding lanthanides, as one would expect from periodic trends, the early actinides up to plutonium have relativistically destabilised and hence delocalised 5f and 6d electrons that participate in chemistry in a similar way to the early transition metals of group 3 through 8: thus, all their valence electrons can participate in chemical reactions, although this is not common for neptunium and plutonium.

<span class="mw-page-title-main">Infrared photodissociation spectroscopy</span>

Infrared photodissociation (IRPD) spectroscopy uses infrared radiation to break bonds in, often ionic, molecules (photodissociation), within a mass spectrometer. In combination with post-ionization, this technique can also be used for neutral species. IRPD spectroscopy has been shown to use electron ionization, corona discharge, and electrospray ionization to obtain spectra of volatile and nonvolatile compounds. Ionized gases trapped in a mass spectrometer can be studied without the need of a solvent as in infrared spectroscopy.

Neptunium compounds are compounds containg the element neptunium (Np). Neptunium has five ionic oxidation states ranging from +3 to +7 when forming chemical compounds, which can be simultaneously observed in solutions. It is the heaviest actinide that can lose all its valence electrons in a stable compound. The most stable state in solution is +5, but the valence +4 is preferred in solid neptunium compounds. Neptunium metal is very reactive. Ions of neptunium are prone to hydrolysis and formation of coordination compounds.

References

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