Uranocene

Last updated
Uranocene
Uranocene-2D-skeletal.png
Uranocene-2D-dimensions.png
Uranocene-3D-vdW.png
Uranocene-3D-balls.png
Names
IUPAC name
Bis(η8-cyclooctatetraenyl)uranium(IV)
Other names
Uranium cyclooctatetraenide
U(COT)2
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/2C8H8.U/c2*1-2-4-6-8-7-5-3-1;/h2*1-8H;/q2*-2;/b2*2-1-,5-3-,8-6-; X mark.svgN
    Key: RHDYKSUWBHNFEJ-GIKYMASMSA-N X mark.svgN
  • InChI=1/2C8H8.U/c2*1-2-4-6-8-7-5-3-1;/h2*1-8H;/q2*-2;/b2*2-1-,5-3-,8-6-;
    Key: RHDYKSUWBHNFEJ-GIKYMASMBM
  • C1=CC=CC=CC=C1.C1=CC=CC=CC=C1.[U]
Properties
C16H16U
Molar mass 446.33 g/mol
Appearancegreen crystals [1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
pyrophoric, radioactive, and toxic
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Uranocene, U(C8H8)2, is an organouranium compound composed of a uranium atom sandwiched between two cyclooctatetraenide rings. It was one of the first organoactinide compounds to be synthesized. It is a green air-sensitive solid that dissolves in organic solvents. Uranocene, a member of the "actinocenes," a group of metallocenes incorporating elements from the actinide series. It is the most studied bis[8]annulene-metal system, although it has no known practical applications. [2]

Contents

Synthesis, structure and bonding

Uranocene was first described in 1968 by the group of Andrew Streitwieser, when it was prepared by the reaction of dipotassium cyclooctatetraenide and uranium tetrachloride in THF at 0°C: [1]

Uranocene synthesis.svg

Uranocene is highly reactive toward oxygen, being pyrophoric in air but stable to hydrolysis. The x-ray crystal structure of uranocene was first elucidated by the group of Ken Raymond. [3] Considering the molecule to be U4+(C8H82−)2, the η8-cyclooctatetraenide groups are planar, as expected for a ring containing 10 π-electrons, and are mutually parallel, forming a sandwich containing the uranium atom. In the solid state, the rings are eclipsed, conferring D8h symmetry on the molecule. In solution the rings rotate with a low activation energy.

The uranium-cyclooctatetraenyl bonding was shown by photoelectron spectroscopy to be primarily due to mixing of uranium 6d orbitals into ligand pi orbitals and therefore donation of electronic charge to the uranium, with a smaller such interaction involving the uranium (5f)2 orbitals. [4] Electronic theory calculations agree with this result [5] [6] and point out that the weaker interaction of the open-shell 5f orbitals with the ligand orbitals determines |MJ|, the magnitude of the angular momentum quantum number along the 8-fold symmetry axis of the ground state. [6]

Spectroscopic properties

Uranocene is paramagnetic. Its magnetic susceptibility is consistent with values of 3 or 4 for |MJ|, with the accompanying magnetic moment being affected by the spin-orbit coupling. [7] Its NMR spectrum is consistent with an |MJ| value of 3. [8] Electronic theory calculations from the simplest [9] to the most accurate [10] also give |MJ| values of 3 for the ground state and 2 for the first excited state, corresponding to double-group symmetry designations [11] of E3g and E2g for these states.

The green color of uranocene is due to three strong transitions in its visible spectrum. [1] [12] In addition to finding vibrational frequencies, Raman spectra indicate the presence of a low-lying (E2g) excited electronic state. [12] [13] On the basis of calculations, [6] the visible transitions are assigned to transitions primarily of 5f-to-6d nature, giving rise to E2u and E3u states.

Analogous compounds

Analogous compounds of the form M(C8H8)2 exist for M = (Nd, Tb, Yb, Th, Pa, Np, and Pu). Extensions include the air-stable derivative U(C8H4Ph4)2 and the cycloheptatrienyl species [U(C7H7)2]. [2] In contrast, bis(cyclooctatetraene)iron has a very different structure, with one each of a η6- and η4-C8H8 ligands.

Related Research Articles

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

A metallocene is a compound typically consisting of two cyclopentadienyl anions (C
5
H
5
, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C5H5)2M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride or vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp2ZrCH3]+ catalyze olefin polymerization.

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

1,3,5,7-Cyclooctatetraene (COT) is an unsaturated derivative of cyclooctane, with the formula C8H8. It is also known as [8]annulene. This polyunsaturated hydrocarbon is a colorless to light yellow flammable liquid at room temperature. Because of its stoichiometric relationship to benzene, COT has been the subject of much research and some controversy.

<span class="mw-page-title-main">Quintuple bond</span> Chemical bond involving ten bonding electrons

A quintuple bond in chemistry is an unusual type of chemical bond, first reported in 2005 for a dichromium compound. Single bonds, double bonds, and triple bonds are commonplace in chemistry. Quadruple bonds are rarer and are currently known only among the transition metals, especially for Cr, Mo, W, and Re, e.g. [Mo2Cl8]4− and [Re2Cl8]2−. In a quintuple bond, ten electrons participate in bonding between the two metal centers, allocated as σ2π4δ4.

<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">Titanocene dichloride</span> Chemical compound

Titanocene dichloride is the organotitanium compound with the formula (η5-C5H5)2TiCl2, commonly abbreviated as Cp2TiCl2. This metallocene is a common reagent in organometallic and organic synthesis. It exists as a bright red solid that slowly hydrolyzes in air. It shows antitumour activity and was the first non-platinum complex to undergo clinical trials as a chemotherapy drug.

<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.

<span class="mw-page-title-main">Organouranium chemistry</span> Area of chemistry

Organouranium chemistry is the science exploring the properties, structure, and reactivity of organouranium compounds, which are organometallic compounds containing a carbon to uranium chemical bond. The field is of some importance to the nuclear industry and of theoretical interest in organometallic chemistry.

<span class="mw-page-title-main">Sextuple bond</span> Covalent bond involving 12 bonding electrons

A sextuple bond is a type of covalent bond involving 12 bonding electrons and in which the bond order is 6. The only known molecules with true sextuple bonds are the diatomic dimolybdenum (Mo2) and ditungsten (W2), which exist in the gaseous phase and have boiling points of 4,639 °C (8,382 °F) and 5,930 °C (10,710 °F) respectively.

Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H-like character (e.g., ZnH2).

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

Ligand bond number (LBN) represents the effective total number of ligands or ligand attachment points surrounding a metal center, labeled M. More simply, it represents the number of coordination sites occupied on the metal. Based on the covalent bond classification method, the equation for determining ligand bond number is as follows:

<span class="mw-page-title-main">Cyclooctatetraenide anion</span> Ion

In chemistry, the cyclooctatetraenide anion or cyclooctatetraenide, more precisely cyclooctatetraenediide, is an aromatic species with a formula of [C8H8]2− and abbreviated as COT2−. It is the dianion of cyclooctatetraene. Salts of the cyclooctatetraenide anion can be stable, e.g., Dipotassium cyclooctatetraenide or disodium cyclooctatetraenide. More complex coordination compounds are known as cyclooctatetraenide complexes, such as the actinocenes.

<span class="mw-page-title-main">Actinocene</span> Class of chemical compounds

Actinocenes are a family of organoactinide compounds consisting of metallocenes containing elements from the actinide series. They typically have a sandwich structure with two dianionic cyclooctatetraenyl ligands (COT2-, which is C
8
H2−
8
) bound to an actinide-metal center (An) in the oxidation state IV, resulting in the general formula An(C8H8)2.

In organometallic chemistry, f-block metallocenes are a class of sandwich compounds consisting of an f-block metal and a set of electron-rich ligands such as the cyclopentadienyl anion.

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

Neptunocene, Np(C8H8)2, is an organoneptunium compound composed of a neptunium atom sandwiched between two cyclooctatetraenide (COT2-) rings. As a solid it has a dark brown/red colour but it appears yellow when dissolved in chlorocarbons, in which it is sparingly soluble. The compound is quite air-sensitive.

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

Plutonocene, Pu(C8H8)2, is an organoplutonium compound composed of a plutonium atom sandwiched between two cyclooctatetraenide (COT2-) rings. It is a dark red, very air-sensitive solid that is sparingly soluble in toluene and chlorocarbons. Plutonocene is a member of the actinocene family of metallocenes incorporating actinide elements in the +4 oxidation state.

<span class="mw-page-title-main">(Pentamethylcyclopentadienyl)aluminium(I)</span> Chemical compound

(Pentamethylcyclopentadienyl)aluminium(I) is an organometallic compound with the formula Al(C5Me5) ("Me" is a methyl group; CH3). The compound is often abbreviated to AlCp* or Cp*Al, where Cp* is the pentamethylcyclopentadienide anion (C5Me5). Discovered in 1991 by Dohmeier et al., AlCp* serves as the first ever documented example of a room temperature stable monovalent aluminium compound. In its isolated form, Cp*Al exists as the tetramer [Cp*Al]4, and is a yellow crystal that decomposes at temperatures above 100 °C but also sublimes at temperatures above 140 °C.

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

A lanthanocene is a type of metallocene compound that contains an element from the lanthanide series. The most common lanthanocene complexes contain two cyclopentadienyl anions and an X type ligand, usually hydride or alkyl ligand.

<span class="mw-page-title-main">Alkaline earth octacarbonyl complex</span> Class of chemical compounds

Alkaline earth octacarbonyl complexes are a class of neutral compounds that have the general formula M(CO)8 where M is a heavy Group 2 element (Ca, Sr, or Ba). The metal center has a formal oxidation state of 0 and the complex has a high level of symmetry belonging to the cubic Oh point group. These complexes are isolable in a low-temperature neon matrix, but are not frequently used in applications due to their instability in air and water. The bonding within these complexes is controversial with some arguing the bonding resembles a model similar to bonding in transition metal carbonyl complexes which abide by the 18-electron rule, and others arguing the molecule more accurately contains ionic bonds between the alkaline earth metal center and the carbonyl ligands. Complexes of Be(CO)8 and Mg(CO)8 are not synthetically possible due to inaccessible (n-1)d orbitals. Beryllium has been found to form a dinuclear homoleptic carbonyl and magnesium a mononuclear heteroleptic carbonyl, both with only two carbonyl ligands instead of eight to each metal atom.

<span class="mw-page-title-main">Organothorium chemistry</span> Study of the carbon-thorium bond

Organothorium chemistry describes the synthesis and properties of organothorium compounds, chemical compounds containing a carbon to thorium chemical bond.

References

  1. 1 2 3 Streitwieser, A.; Mueller-Westerhoff, U. (1968). "Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals". J. Am. Chem. Soc. 90 (26): 7364. doi:10.1021/ja01028a044.
  2. 1 2 Seyferth, D. (2004). "Uranocene. The First Member of a New Class of Organometallic Derivatives of the f Elements". Organometallics . 23 (15): 3562–3583. doi:10.1021/om0400705.
  3. Zalkin, Allan; Raymond, Kenneth N. (1969). "Structure of di-.pi.-cyclooctatetraeneuranium (uranocene)". Journal of the American Chemical Society. 91 (20): 5667–5668. doi:10.1021/ja01048a055. ISSN   0002-7863.
  4. Clark, J. P.; Green, J. C. (1977). "An Investigation of the Electronic Structure of Bis(eta-cyclo-octatetraene)-actinoids by Helium-(I) and -(II) Photoelectron Spectroscopy". J. Chem. Soc., Dalton Trans. (5): 505–508. doi:10.1039/DT9770000505.
  5. Roesch, N.; Streitwieser, A. (1983). "Quasirelativistic SCF-Xalpha Scattered-Wave Study of Uranocene, Thorocene, and Cerocene". J. Am. Chem. Soc. 105 (25): 7237–7240. doi:10.1021/ja00363a004.
  6. 1 2 3 Chang, A. H. H.; Pitzer, R. M. (1989). "Electronic Structure and Spectra of Uranocene". J. Am. Chem. Soc. 111 (7): 2500–2507. doi:10.1021/ja00189a022.
  7. Karraker, D. G.; Stone, J. A.; Jones, E. R.; Edelstein, N. (1970). "Bis(cyclooctatetraenyl)neptunium(IV) and Bis(cyclooctatetraenyl)plutonium(IV)". J. Chem. Phys. 92 (16): 4841–4845. doi:10.1021/ja00719a014.
  8. Fischer, R. D. (1979). "NMR Spectroscopy of Organometallic Compounds of the f-Elements: Practical Applications". In Marks, T. J.; Fischer, R. D. (eds.). Volume 44 – Organometallics of the f-Elements. NATO Advanced Study Institutes Series: Series C – Mathematical and Physical Sciences. Dordrecht, Holland: Reidel. pp. 337–377. ISBN   90-277-0990-4.
  9. Hayes, R. G.; Edelstein, N. (1972). "An Elementary Molecular Orbital Calculation on U(C8H8)2 and Its Application to the Electronic Structure of U(C8H8)2, Np(C8H8)2. and Pu(C8H8)2". J. Am. Chem. Soc. 94 (25): 8688–8691. doi:10.1021/ja00780a008.
  10. Liu, W.; Dolg, M.; Fulde, P. (1997). "Low-lying electronic states of lanthanocenes and actinocenes M(C8H8)2 (M=Nd, Tb, Yb, U)". J. Chem. Phys. 107 (9): 3584–3591. Bibcode:1997JChPh.107.3584L. doi:10.1063/1.474698.
  11. Herzberg, G. (1966). Molecular Spectra and Molecular Structure III. Electronic Spectra and Electronic Structure of Polyatomic Molecules. Princeton, New Jersey: D. Van Nostrand. p. 566.
  12. 1 2 Dallinger, R. F.; Stein, P.; Spiro, T. G. (1978). "Resonance Raman Spectroscopy of Uranocene: Observation of an Anomalously Polarized Electronic Band and Assignment of Energy Levels". J. Am. Chem. Soc. 100 (25): 7865–7870. doi:10.1021/ja00493a013.
  13. Hager, J. S.; Zahardis, J.; Pagni, R. M.; et al. (2004). "Raman under nitrogen. The high-resolution Raman spectroscopy of crystalline uranocene, thorocene, and ferrocene". J. Chem. Phys. 120 (6): 2708–2718. Bibcode:2004JChPh.120.2708H. doi:10.1063/1.1637586. PMID   15268415.

Further reading