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

<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.

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 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 organometallic group 2 compounds are rare and are typically limited to academic interests.

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

Organozirconium chemistry is the science of exploring the properties, structure, and reactivity of organozirconium compounds, which are organometallic compounds containing chemical bonds between carbon and zirconium. Organozirconium compounds have been widely studied, in part because they are useful catalysts in Ziegler-Natta polymerization.

Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.

<span class="mw-page-title-main">Organoscandium chemistry</span> Chemistry of compounds containing a carbon to scandium chemical bond

Organoscandium chemistry is an area with organometallic compounds focused on compounds with at least one carbon to scandium chemical bond. The interest in organoscandium compounds is mostly academic but motivated by potential practical applications in catalysis, especially in polymerization. A common precursor is scandium chloride, especially its THF complex.

<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.

Organolanthanide chemistry is the field of chemistry that studies organolanthanides, compounds with a lanthanide-to-carbon bond. Organolanthanide compounds are different from their organotransition metal analogues in the following ways:

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

Organocerium chemistry is the science of organometallic compounds that contain one or more chemical bond between carbon and cerium. These compounds comprise a subset of the organolanthanides. Most organocerium compounds feature Ce(III) but some Ce(IV) derivatives are known.

<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 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">Half sandwich compound</span> Class of coordination compounds

Half sandwich compounds, also known as piano stool complexes, are organometallic complexes that feature a cyclic polyhapto ligand bound to an MLn center, where L is a unidentate ligand. Thousands of such complexes are known. Well-known examples include cyclobutadieneiron tricarbonyl and (C5H5)TiCl3. Commercially useful examples include (C5H5)Co(CO)2, which is used in the synthesis of substituted pyridines, and methylcyclopentadienyl manganese tricarbonyl, an antiknock agent in petrol.

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.

Magnesocene, also known as bis(cyclopentadienyl)magnesium(II) and sometimes abbreviated as MgCp2, is an organometallic compound with the formula Mg(η5-C5H5)2. It is an example of an s-block main group sandwich compound, structurally related to the d-block element metallocenes, and consists of a central magnesium atom sandwiched between two cyclopentadienyl rings.

<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.

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

Trimesitylvanadium (mesityl or Mes = 2,4,6-trimethylphenyl) is one of the organovanadium complexes with vanadium in an oxidation state of 3. This compound was first synthesized by W. Seidel and G. Kreisel in 1974. To prepare this compound, VCl3(THF)3 (THF = tetrahydrofuran) was reacted with Grignard reagent MesMgBr to form a blue solution at room temperature. It is precipitated by the addition of dioxane, which results in a blue solid. It is thermally stable, but it is also an air-sensitive compound.

References

  1. Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. 1997
  2. Kotohiro Nomura; Shu Zhang (2011). "Design of Vanadium Complex Catalysts for Precise Olefin Polymerization". Chem. Rev. 111 (3): 2342–2362. doi:10.1021/cr100207h. PMID   21033737.
  3. Wilkinson, G.; Birmingham, J. G. (1954). "Bis-cyclopentadienyl Compounds of Ti, Zr, V, Nb and Ta". Journal of the American Chemical Society . 76 (17): 4281–4284. doi:10.1021/ja01646a008.
  4. Fischer, Ernst Otto; Schneider, Robert J. J. (1970). "Über Aromatenkomplexe von Metallen, CXIV. Darstellung und Reaktionen von Dicyclopentadienyl-divanadin-pentacarbonyl, (C 5 H 5 ) 2 V 2 (CO) 5". Chemische Berichte. 103 (11): 3684–3695. doi:10.1002/cber.19701031133.
  5. Robert Choukroun, Christian Lorber (2005). "Adventures in Vanadocene Chemistry". Eur. J. Inorg. Chem. 2005 (23): 4683–4692. doi:10.1002/ejic.200500371.
  6. King, R.B.; Stone, F.G.A (1963). "Cyclopentadienyl Metal Carbonyls and Some Derivatives". Inorganic Syntheses. Vol. 7. pp. 99–115. doi:10.1002/9780470132388.ch31. ISBN   978-0-470-13238-8.{{cite book}}: |journal= ignored (help)
  7. Vivanco, M.; Ruiz, J.; Floriani, C.; Chiesi-Villa, A.; Rizzoli, C. "Chemistry of the vanadium-carbon .sigma. bond. 1. Insertion of carbon monoxide, isocyanides, carbon dioxide, and heterocumulenes into the V-C bond of Tris(mesityl)vanadium(III)" Organometallics 1993 volume 12, 1794–1801. doi : 10.1021/om00029a042
  8. Toshikazu Hirao (1997). "Vanadium in Modern Organic Synthesis". Chemical Reviews. 97 (8): 2707–2724. doi:10.1021/cr960014g. PMID   11851478.
  9. Kotohiro Nomura; Shu Zhang (2011). "Design of Vanadium Complex Catalysts for Precise Olefin Polymerization". Chem. Rev. 111 (3): 2342–2362. doi:10.1021/cr100207h. PMID   21033737.
  10. Werner Obrecht; Jean-Pierre Lambert; Michael Happ; Christiane Oppenheimer-Stix; John Dunn; Ralf Krüger (2012). "Rubber, 4. Emulsion Rubber". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.o23_o01. ISBN   978-3527306732.