Organovanadium chemistry

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Organovanadium chemistry is the chemistry of organometallic compounds containing a carbon (C) to vanadium (V) chemical bond. [1] Organovanadium compounds find only minor use as reagents in organic synthesis but are significant for polymer chemistry as catalysts. [2]

Contents

Oxidation states for vanadium are +2, +3, +4 and +5. Low valency vanadium is usually stabilized with carbonyl ligands. Oxo derivatives are relatively common, unlike the organic complexes of neighboring elements.

Compound classes

Carbonyls

Vanadium carbonyl can be prepared by reductive carbonylation of vanadium salts:

4 Na + VCl3 + 6 CO → Na[V(CO)6] + 3 NaCl

The salt can be oxidized to the 17e binary carbonyl V(CO)6.

Cyclopentadienyl derivatives

(Cycloheptatrienyl)(cyclopentadienyl)vanadium is one of many organovanadium compounds that is paramagnetic. Trovacene.svg
(Cycloheptatrienyl)(cyclopentadienyl)vanadium is one of many organovanadium compounds that is paramagnetic.

Vanadocene dichloride, the first organovanadium complexes to be reported, [3] is prepared from sodium cyclopentadienyl and vanadium tetrachloride:

2 NaC5H5 + VCl4 → VCp2Cl2 + 2NaCl

Reduction of this compound gives the parent vanadocene (Cp2V):

VCp2Cl2 + LiAlH4 → VCp2
Cp2V2(CO)5 featuring a pair of semi-bridging CO ligands. CPPCDV01.png
Cp2V2(CO)5 featuring a pair of semi-bridging CO ligands.

Vanadocene is the lightest transition metal metallocene that is isolable at room temperature. [5] Vanadocene reacts with high pressures of carbon monoxide to give CpV(CO)4. [6] Photolysis of the tetracarbonyl gives Cp2V2(CO)5. Several analogous indenyl complexes are known.

Monocyclopentadienyl vanadium chlorides include CpVCl3 and the diamagnetic CpVOCl2.

Arene complexes

Vanadium forms a variety of arene complexes, e.g. with benzene:

VCl4 + Al + 2 C6H6 → [V(η6-C6H6)2]AlCl4
[V(η6-C6H6)2]AlCl4 + H2O → V(η6-C6H6)2 + ...

Alkyl and aryl derivatives

A handful of alkyl and aryl complexes exist. The reactive species V(mesityl)3 forms from VCl3: [7]

VCl3(THF)3 + 3 LiC6H2-2,4,6-Me3 → V(C6H2-2,4,6-Me3)3(THF) + 3 LiCl

This species binds CO and, under appropriate conditions, N2. V(mesityl)3 adds a fourth mesityl group and the resulting "ate complex" can be oxidized to the vanadium(IV) derivative:

V(mes)3(THF) + LiMes → Li[V(mes)4]
Li[V(mes)4] + air → V(mes)4(THF)

The tetrakis(norbornyl) complex is also known.

Vanadium oxytrichloride is a starting material for organovanadium(IV) and organovanadium(V) compounds:

VOCl3 + Li(mes) → Li[VO(mes)3]
Li[VO(mes)3] + chloranil → VO(mes)3
VOCl3 + ZnPh2 → VOPhCl2 + "ZnPh(Cl)"

Catalysts and reagents

Well-defined vanadium compounds do not appear as catalysts in any commercial process. [8] However organovanadium species are clearly implicated as catalysts for the production of butadiene-based rubbers. These catalysts are generated in situ by treating soluble coordination complexes such as vanadium(III) acetylacetonate with organoaluminium activators. [9] [10]

Related Research Articles

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Titanium tetrachloride is the inorganic compound with the formula TiCl4. It is an important intermediate in the production of titanium metal and the pigment titanium dioxide. TiCl4 is a volatile liquid. Upon contact with humid air, it forms thick clouds of titanium dioxide and hydrochloric acid, a reaction that was formerly exploited for use in smoke machines. It is sometimes referred to as “tickle” or “tickle 4”, as a phonetic representation of the symbols of its molecular formula.

<span class="mw-page-title-main">Cyclopentadienyl complex</span> Coordination complex of a metal and Cp⁻ ions

A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups. Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring.

Vanadocene dichloride is an organometallic complex with formula (η5-C5H5)2VCl2 (commonly abbreviated as Cp2VCl2). It is a structural analogue of titanocene dichloride but with vanadium(IV) instead of titanium(IV). This compound has one unpaired electron, hence Cp2VCl2 is paramagnetic. Vanadocene dichloride is a suitable precursor for variety of bis(cyclopentadienyl)vanadium(IV) compounds.

Vanadium tetrachloride is the inorganic compound with the formula VCl4. This reddish-brown liquid serves as a useful reagent for the preparation of other vanadium compounds.

<span class="mw-page-title-main">Vanadium(III) chloride</span> Chemical compound

Vanadium(III) chloride is the inorganic compound with the formula VCl3 which forms the hexahydrate, [VCl2(H2O)4]Cl·2H2O. This hygroscopic purple salt is a common precursor to other vanadium(III) complexes.

<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">Organotitanium chemistry</span>

Organotitanium chemistry is the science of organotitanium compounds describing their physical properties, synthesis, and reactions. Organotitanium compounds in organometallic chemistry contain carbon-titanium chemical bonds. They are reagents in organic chemistry and are involved in major industrial processes.

<span class="mw-page-title-main">Group 2 organometallic chemistry</span>

Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organmetallic group 2 compounds are rare and are typically limited to academic interests.

<span class="mw-page-title-main">Organozirconium and organohafnium chemistry</span>

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

Organorhodium chemistry is the chemistry of organometallic compounds containing a rhodium-carbon chemical bond, and the study of rhodium and rhodium compounds as catalysts in organic reactions.

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

Vanadocene, bis(η5-cyclopentadienyl) vanadium, is the organometallic compound with the formula V(C5H5)2, commonly abbreviated Cp2V. It is a violet crystalline, paramagnetic solid. Vanadocene has relatively limited practical use, but it has been extensively studied.

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

Metal bis(trimethylsilyl)amides are coordination complexes composed of a cationic metal with anionic bis(trimethylsilyl)amide ligands and are part of a broader category of metal amides.

<span class="mw-page-title-main">Half sandwich compound</span> Class of coordination compounds

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

Tetramesityldiiron is an organoiron compound with the formula Fe2(C6H2(CH3)3)4. It is a red, air-sensitive solid that is used as a precursor to other iron complexes. It adopts a centrosymmetric structure. The complex is a Lewis acid, forming monomeric adducts, e.g. Fe(C6H2(CH3)3)2pyridine2. The complex is prepared by treating ferrous halides with the Grignard reagent formed from mesityl bromide:

Organoniobium chemistry is the chemistry of compounds containing niobium-carbon (Nb-C) bonds. Compared to the other group 5 transition metal organometallics, the chemistry of organoniobium compounds most closely resembles that of organotantalum compounds. Organoniobium compounds of oxidation states +5, +4, +3, +2, +1, 0, -1, and -3 have been prepared, with the +5 oxidation state being the most common.

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<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">Cyclopentadienylvanadium tetracarbonyl</span> Chemical compound

Cyclopentadienylvanadium tetracarbonyl is the organovanadium compound with the formula (C5H5)V(CO)4. An orange, diamagnetic solid, it is the principal cyclopentadienyl carbonyl of vanadium. It can be prepared by heating a solution of vanadocene under high pressure of carbon monoxide. As confirmed by X-ray crystallography, the coordination sphere of vanadium consists of η5-cyclopentadienyl and four carbonyl ligands. The molecule is a four-legged piano stool complex. The compound is soluble in common organic solvents. The compound has no commercial applications.

References

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