Uranium hexoxide

Last updated
Uranium hexoxide
Identifiers
3D model (JSmol)
  • InChI=1S/6O.U
    Key: LOXQZMJDQSSDDQ-UHFFFAOYSA-N
  • O=[U](=O)(=O)(=O)(=O)=O
Properties
UO6
Molar mass 334.0288 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Uranium hexoxide is an unusual, theoretically possible compound of uranium in which the uranium atom would be attached to six oxygen atoms. [1] [2] It would be an unprecedented example of an element in the +12 oxidation state; [1] for comparison, the highest known oxidation state is +9 for iridium in the cation IrO+
4
. [3] [4] This oxidation state assignment requires participation of 6p electrons of uranium as valence electrons. This assertion was disputed by a later paper, [2] which formulates the octahedral species as O(–I) and U(VI), although it does acknowledge that the question of valence shell expansion of uranium and other actinoids is complex and that the "semi-core" 6p electrons of uranium are involved to a non-negligible extent in the bonding of structures such as octahedral UO6.

Structure

Uranium hexoxide is predicted to have octahedral symmetry; however, other forms have been studied. In the 1Oh the oxygen atoms are oxide ions (O2−). In the 1D3 form there are three peroxide ions (O2−
2
). The 3D2h form has two oxo oxygens and two pairs of superoxide (O
2
). The octahedral form was calculated to be less energetically favorable than the other geometries though still predicted to be a local energy minimum. [2]

Related Research Articles

<span class="mw-page-title-main">Oxide</span> Chemical compound where oxygen atoms are combined with atoms of other elements

An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.

In chemistry, a transition metal is a chemical element in the d-block of the periodic table, though the elements of group 12 are sometimes excluded. The lanthanide and actinide elements are called inner transition metals and are sometimes considered to be transition metals as well.

In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to other atoms were fully ionic. It describes the degree of oxidation of an atom in a chemical compound. Conceptually, the oxidation state may be positive, negative or zero. While fully ionic bonds are not found in nature, many bonds exhibit strong ionicity, making oxidation state a useful predictor of charge.

In chemistry, a reducing agent is a chemical species that "donates" an electron to an electron recipient. Examples of substances that are common reducing agents include hydrogen, the alkali metals, formic acid, oxalic acid, and sulfite compounds.

An oxyanion, or oxoanion, is an ion with the generic formula A
x
Oz
y
. Oxyanions are formed by a large majority of the chemical elements. The formulae of simple oxyanions are determined by the octet rule. The corresponding oxyacid of an oxyanion is the compound H
z
A
x
O
y
. The structures of condensed oxyanions can be rationalized in terms of AOn polyhedral units with sharing of corners or edges between polyhedra. The oxyanions adenosine monophosphate (AMP), adenosine diphosphate (ADP) and adenosine triphosphate (ATP) are important in biology.

<span class="mw-page-title-main">VSEPR theory</span> Model for predicting molecular geometry

Valence shell electron pair repulsion (VSEPR) theory is a model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. It is also named the Gillespie-Nyholm theory after its two main developers, Ronald Gillespie and Ronald Nyholm.

<span class="mw-page-title-main">Vaska's complex</span> Chemical compound

Vaska's complex is the trivial name for the chemical compound trans-carbonylchlorobis(triphenylphosphine)iridium(I), which has the formula IrCl(CO)[P(C6H5)3]2. This square planar diamagnetic organometallic complex consists of a central iridium atom bound to two mutually trans triphenylphosphine ligands, carbon monoxide and a chloride ion. The complex was first reported by J. W. DiLuzio and Lauri Vaska in 1961. Vaska's complex can undergo oxidative addition and is notable for its ability to bind to O2 reversibly. It is a bright yellow crystalline solid.

<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.

The bond valencemethod or mean method is a popular method in coordination chemistry to estimate the oxidation states of atoms. It is derived from the bond valence model, which is a simple yet robust model for validating chemical structures with localized bonds or used to predict some of their properties. This model is a development of Pauling's rules.

The 18-electron rule is a chemical rule of thumb used primarily for predicting and rationalizing formulas for stable transition metal complexes, especially organometallic compounds. The rule is based on the fact that the valence orbitals in the electron configuration of transition metals consist of five (n−1)d orbitals, one ns orbital, and three np orbitals, where n is the principal quantum number. These orbitals can collectively accommodate 18 electrons as either bonding or non-bonding electron pairs. This means that the combination of these nine atomic orbitals with ligand orbitals creates nine molecular orbitals that are either metal-ligand bonding or non-bonding. When a metal complex has 18 valence electrons, it is said to have achieved the same electron configuration as the noble gas in the period, lending stability to the complex. Transition metal complexes that deviate from the rule are often interesting or useful because they tend to be more reactive. The rule is not helpful for complexes of metals that are not transition metals. The rule was first proposed by American chemist Irving Langmuir in 1921.

<span class="mw-page-title-main">Hypofluorous acid</span> Chemical compound

Hypofluorous acid, chemical formula HOF, is the only known oxyacid of fluorine and the only known oxoacid in which the main atom gains electrons from oxygen to create a negative oxidation state. The oxidation state of the oxygen in this acid is 0, while its valence is 2. It is also the only hypohalous acid that can be isolated as a solid. HOF is an intermediate in the oxidation of water by fluorine, which produces hydrogen fluoride, oxygen difluoride, hydrogen peroxide, ozone and oxygen. HOF is explosive at room temperature, forming HF and O2:

A hexafluoride is a chemical compound with the general formula QXnF6, QXnF6m−, or QXnF6m+. Many molecules fit this formula. An important hexafluoride is hexafluorosilicic acid (H2SiF6), which is a byproduct of the mining of phosphate rock. In the nuclear industry, uranium hexafluoride (UF6) is an important intermediate in the purification of this element.

<span class="mw-page-title-main">Dichlorine hexoxide</span> Chemical compound

Dichlorine hexoxide is the chemical compound with the molecular formula Cl
2
O
6
, which is correct for its gaseous state. However, in liquid or solid form, this chlorine oxide ionizes into the dark red ionic compound chloryl perchlorate [ClO
2
]+
[ClO
4
]
, which may be thought of as the mixed anhydride of chloric and perchloric acids.

A transition metal oxo complex is a coordination complex containing an oxo ligand. Formally O2-, an oxo ligand can be bound to one or more metal centers, i.e. it can exist as a terminal or (most commonly) as bridging ligands (Fig. 1). Oxo ligands stabilize high oxidation states of a metal. They are also found in several metalloproteins, for example in molybdenum cofactors and in many iron-containing enzymes. One of the earliest synthetic compounds to incorporate an oxo ligand is potassium ferrate (K2FeO4), which was likely prepared by Georg E. Stahl in 1702.

Transition metal oxides are compounds composed of oxygen atoms bound to transition metals. They are commonly utilized for their catalytic activity and semiconducting properties. Transition metal oxides are also frequently used as pigments in paints and plastics, most notably titanium dioxide. Transition metal oxides have a wide variety of surface structures which affect the surface energy of these compounds and influence their chemical properties. The relative acidity and basicity of the atoms present on the surface of metal oxides are also affected by the coordination of the metal cation and oxygen anion, which alter the catalytic properties of these compounds. For this reason, structural defects in transition metal oxides greatly influence their catalytic properties. The acidic and basic sites on the surface of metal oxides are commonly characterized via infrared spectroscopy, calorimetry among other techniques. Transition metal oxides can also undergo photo-assisted adsorption and desorption that alter their electrical conductivity. One of the more researched properties of these compounds is their response to electromagnetic radiation, which makes them useful catalysts for redox reactions, isotope exchange and specialized surfaces.

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.

Iridium tetroxide (IrO4, Iridium(VIII) oxide) is a binary compound of oxygen and iridium in oxidation state +8. This compound was formed by photochemical rearrangement of [(η1-O2)IrO2] in solid argon at a temperature of 6 K (−267.15 °C; −448.87 °F). At higher temperatures, the oxide is unstable. The detection of the iridium tetroxide cation IrO+
4
by infrared photodissociation spectroscopy with formal oxidation state +9 has been reported, the highest currently known of any element. However no salts are known, as attempted production of an Ir(IX) salt such as IrO4SbF6 did not result in anything.

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

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.

Argon compounds, the chemical compounds that contain the element argon, are rarely encountered due to the inertness of the argon atom. However, compounds of argon have been detected in inert gas matrix isolation, cold gases, and plasmas, and molecular ions containing argon have been made and also detected in space. One solid interstitial compound of argon, Ar1C60 is stable at room temperature. Ar1C60 was discovered by the CSIRO.

Iridium compounds are compounds containing the element iridium (Ir). Iridium forms compounds in oxidation states between −3 and +9, but the most common oxidation states are +1, +2, +3, and +4. Well-characterized compounds containing iridium in the +6 oxidation state include IrF6 and the oxides Sr2MgIrO6 and Sr2CaIrO6. iridium(VIII) oxide was generated under matrix isolation conditions at 6 K in argon. The highest oxidation state (+9), which is also the highest recorded for any element, is found in gaseous [IrO4]+.

References

  1. 1 2 Pyykkö, P.; Runeberg, N.; Straka, M.; Dyall, K. G. (2000). "Could uranium(XII)hexoxide, UO6 (Oh) exist?" (PDF). Chemical Physics Letters. 328 (4–6): 415–419. Bibcode:2000CPL...328..415P. doi:10.1016/S0009-2614(00)00958-1.[ permanent dead link ]
  2. 1 2 3 Xiao, H.; Hu, H. S.; Schwarz, W. H. E.; Li, J. (2010). "Theoretical Investigations of Geometry, Electronic Structure and Stability of UO6: Octahedral Uranium Hexoxide and Its Isomers". The Journal of Physical Chemistry A. 114 (33): 8837–8844. doi:10.1021/jp102107n. PMID   20572656.
  3. Wang, Guanjun; Zhou, Mingfei; Goettel, James T.; Schrobilgen, Gary J.; Su, Jing; Li, Jun; Schlöder, Tobias; Riedel, Sebastian (23 October 2014). "Identification of an iridium-containing compound with a formal oxidation state of IX". Nature. 514 (7523): 475–477. Bibcode:2014Natur.514..475W. doi:10.1038/nature13795. PMID   25341786. S2CID   4463905.
  4. Himmel, D.; Knapp, C.; Patzschke, M.; Riedel, S. (2010). "How far can we go? Quantum-chemical investigations of oxidation state IX". ChemPhysChem. 11 (4): 865–869. doi:10.1002/cphc.200900910. PMID   20127784.