Organothorium chemistry

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Structure of thorocene Uranocene-3D-balls.png
Structure of thorocene

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

Most of the work on organothorium compounds has focused on the cyclopentadienyls and cyclooctatetraenyls. Like many of the early and middle actinides (thorium through americium, and also expected for curium), thorium forms the yellow cyclooctatetraenide complex Th(C
8
H
8
)
2
, thorocene. It is isotypic with the more well-known analogous uranium compound, uranocene. [1] Although these f-series cyclooctatetraenyls are not isotypic with the d-series cyclopentadienyls, including the more famous ferrocene, they have very similar structures, and were named to emphasise this resemblance. [2] It can be prepared by reacting K2C8H8 with thorium tetrachloride in tetrahydrofuran (THF) at the temperature of dry ice, or by reacting thorium tetrafluoride with MgC8H8. [1] It is an unstable compound in air and outright decomposes in water or at 190 °C. [1] Half-sandwich compounds are also known, such as 2(η8-C8H8)ThCl2(THF)2, which has a piano-stool structure and is made by reacting thorocene with thorium tetrachloride in tetrahydrofuran. [3]

The simplest of the cyclopentadienyls are ThIII(C
5
H
5
)
3
and ThIV(C
5
H
5
)
4
: many derivatives are known. The first (which has two forms, one purple and one green) is a rare example of thorium in the formal +3 oxidation state. [2] [1] In the derivative [ThIII{η5-C5H3(SiMe3)2}3], a blue paramagnetic compound, the molecular geometry is trigonal planar around the thorium atom, which has a [Rn]6d1 configuration instead of the expected [Rn]5f1. [ThIII{η5-C5H3(SiMe3)2}3] can be reduced to the anion [ThII{η5-C5H3(SiMe3)2}3], in which thorium exhibits a very rare +2 oxidation state. [4] The second is prepared by heating thorium tetrachloride with K(C
5
H
5
)
under reflux in benzene: the four cyclopentadienyl rings are arranged tetrahedrally around the central thorium atom. The halide derivative Th(C
5
H
5
)
3
Cl
can be made similarly by reducing the amount of K(C
5
H
5
)
used (other univalent metal cyclopentadienyls can also be used), and the chlorine atom may be further replaced by other halogens or by alkoxy, alkyl, aryl, or BH4 groups. Of these, the alkyl and aryl derivatives have been investigated more deeply due to the insight they give regarding the nature of the Th–C σ bond. [2] Of special interest is the dimer [Th(η5-C5H5)2-μ-(η5,η1-C5H5)]2, where the two thorium atoms are bridged by two cyclopentadienyl rings, similarly to the structure of niobocene. [2]

Tetrabenzylthorium, Th(CH
2
C
6
H
5
)
, is known, but its structure has not yet been determined. Thorium forms the monocapped trigonal prismatic anion [Th(CH3)7]3−, heptamethylthorate, which forms the salt [Li(tmeda)]3[ThMe7] (tmeda = Me2NCH2CH2NMe2). Although one methyl group is only attached to the thorium atom (Th–C distance 257.1 pm) and the other six connect the lithium and thorium atoms (Th–C distances 265.5–276.5 pm) they behave equivalently in solution. Tetramethylthorium, Th(CH
3
)
4
, is not known, but its adducts are stabilised by phosphine ligands. [3]

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">Thorium</span> Chemical element, symbol Th and atomic number 90

Thorium is a chemical element. It has the symbol Th and atomic number 90. Thorium is a weakly radioactive light silver metal which tarnishes olive gray when it is exposed to air, forming thorium dioxide; it is moderately soft and malleable and has a high melting point. Thorium is an electropositive actinide whose chemistry is dominated by the +4 oxidation state; it is quite reactive and can ignite in air when finely divided.

Ferrocene is an organometallic compound with the formula Fe(C5H5)2. The molecule is a complex consisting of two cyclopentadienyl rings sandwiching a central iron atom. It is an orange solid with a camphor-like odor that sublimes above room temperature, and is soluble in most organic solvents. It is remarkable for its stability: it is unaffected by air, water, strong bases, and can be heated to 400 °C without decomposition. In oxidizing conditions it can reversibly react with strong acids to form the ferrocenium cation Fe(C5H5)+2. Ferrocene and the ferrocenium cation are sometimes abbreviated as Fc and Fc+ respectively.

Cyclopentadiene is an organic compound with the formula C5H6. It is often abbreviated CpH because the cyclopentadienyl anion is abbreviated Cp.

<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">Hapticity</span> Number of contiguous atoms in a ligand that bond to the central atom in a coordination complex

In coordination chemistry, hapticity is the coordination of a ligand to a metal center via an uninterrupted and contiguous series of atoms. The hapticity of a ligand is described with the Greek letter η ('eta'). For example, η2 describes a ligand that coordinates through 2 contiguous atoms. In general the η-notation only applies when multiple atoms are coordinated. In addition, if the ligand coordinates through multiple atoms that are not contiguous then this is considered denticity, and the κ-notation is used once again. When naming complexes care should be taken not to confuse η with μ ('mu'), which relates to bridging ligands.

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

Chromocene is the organochromium compound with the formula [Cr(C5H5)2]. Like structurally related metallocenes, chromocene readily sublimes in a vacuum and is soluble in non-polar organic solvents. It is more formally known as bis(η5-cyclopentadienyl)chromium(II).

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.

<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.

Nomenclature of Inorganic Chemistry, IUPAC Recommendations 2005 is the 2005 version of Nomenclature of Inorganic Chemistry. It is a collection of rules for naming inorganic compounds, as recommended by the International Union of Pure and Applied Chemistry (IUPAC).

In organometallic chemistry, a transition metal indenyl complex is a coordination compound that contains one or more indenyl ligands. The indenyl ligand is formally the anion derived from deprotonation of indene. The η5-indenyl ligand is related to the η5cyclopentadienyl anion (Cp), thus indenyl analogues of many cyclopentadienyl complexes are known. Indenyl ligands lack the 5-fold symmetry of Cp, so they exhibit more complicated geometries. Furthermore, some indenyl complexes also exist with only η3-bonding mode. The η5- and η3-bonding modes sometimes interconvert.

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

Sodium cyclopentadienide is an organosodium compound with the formula C5H5Na. The compound is often abbreviated as NaCp, where Cp is the cyclopentadienide anion. Sodium cyclopentadienide is a colorless solid, although samples often are pink owing to traces of oxidized impurities.

<span class="mw-page-title-main">Rhodocene</span> Organometallic chemical compound

Rhodocene is a chemical compound with the formula [Rh(C5H5)2]. Each molecule contains an atom of rhodium bound between two planar aromatic systems of five carbon atoms known as cyclopentadienyl rings in a sandwich arrangement. It is an organometallic compound as it has (haptic) covalent rhodium–carbon bonds. The [Rh(C5H5)2] radical is found above 150 °C (302 °F) or when trapped by cooling to liquid nitrogen temperatures (−196 °C [−321 °F]). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.

<span class="mw-page-title-main">Metal bis(trimethylsilyl)amides</span>

Metal bis(trimethylsilyl)amides are coordination complexes composed of a cationic metal M with anionic bis(trimethylsilyl)amide ligands (the N 2 monovalent anion, or −N 2 monovalent group, and are part of a broader category of metal amides.

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

<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.

<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.

<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.

Protactinium compounds are compounds containing the element protactinium. These compounds usually have protactinium in the +5 oxidation state, although these compounds can also exist in the +2, +3 and +4 oxidation states.

References

  1. 1 2 3 4 Wickleder et al., pp. 116–7
  2. 1 2 3 4 Greenwood and Earnshaw, pp. 1278–80
  3. 1 2 Cotton, Simon (2006). Lanthanide and Actinide Chemistry. John Wiley & Sons Ltd.
  4. Langeslay, Ryan R.; Fieser, Megan E.; Ziller, Joseph W.; Furche, Philip; Evans, William J. (2015). "Synthesis, structure, and reactivity of crystalline molecular complexes of the {[C5H3(SiMe3)2]3Th}1− anion containing thorium in the formal +2 oxidation state". Chem. Sci. 6 (1): 517–521. doi:10.1039/C4SC03033H. PMC   5811171 . PMID   29560172.

Bibliography