Organovanadium chemistry

<h2 id="compound-classes">Compound classes</h2>
<h3>Carbonyls</h3>
<p><a href="/facts/Vanadium_carbonyl/Fn1PuRPk">Vanadium carbonyl</a> can be prepared by reductive <a href="/facts/Carbonylation/Jq8jghNR">carbonylation</a> of vanadium salts:
</p>
4 Na + VCl3 + 6 CO → Na[V(CO)6] + 3 NaCl
<p>The salt can be oxidized to the 17e binary carbonyl V(CO)6.
</p>
<h3>Cyclopentadienyl derivatives</h3>

<p><a href="/facts/Vanadocene_dichloride/lUe2BJ3q">Vanadocene dichloride</a>, the first organovanadium complexes to be reported,<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a> is prepared from <a href="/facts/Sodium_cyclopentadienyl/l7JaX1NP">sodium cyclopentadienyl</a> and <a href="/facts/Vanadium_tetrachloride/evQC8Yzp">vanadium tetrachloride</a>:
</p>
2 NaC5H5 + VCl4 → VCp2Cl2 + 2NaCl
<p>Reduction of this compound gives the parent <a href="/facts/Vanadocene/SL6oneuQ">vanadocene</a> (Cp2V):
</p>
VCp2Cl2 + LiAlH4 → VCp2

<p><a href="/facts/Vanadocene/SL6oneuQ">Vanadocene</a> is the lightest <a href="/facts/Transition_metal/0slGWoLQ">transition metal</a> <a href="/facts/Metallocene/AecA5Qrk">metallocene</a> that is isolable at room temperature.<a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> Vanadocene reacts with high pressures of carbon monoxide to give <a href="/facts/Cyclopentadienylvanadium_tetracarbonyl/MbLTUpTu">CpV(CO)4</a>.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> <a href="/facts/Photodissociation/nzRyzh8I">Photolysis</a> of the tetracarbonyl gives Cp2V2(CO)5. Several analogous <a href="/facts/Indenyl_complex/UovkVaQK">indenyl complexes</a> are known.  
</p><p>Monocyclopentadienyl vanadium chlorides include CpVCl3 and the diamagnetic CpVOCl2.
</p>
<h3>Arene complexes</h3>
<p>Vanadium forms a variety of <a href="/facts/Arene/S5lpGPsm">arene</a> complexes, e.g. with <a href="/facts/Benzene/Fguue7nr">benzene</a>:
</p>
VCl4  +  Al  +  2 C6H6   →   [V(η6-C6H6)2]AlCl4
[V(η6-C6H6)2]AlCl4  +  H2O  →  V(η6-C6H6)2  +  ...
<h3>Alkyl and aryl derivatives</h3>
<p>A handful of <a href="/facts/Alkyl/vmEk8X4v">alkyl</a> and <a href="/facts/Aryl/M3z7QRXd">aryl</a> complexes exist. The reactive species V(<a href="/facts/Mesitylene/4JCRbj1Y">mesityl</a>)3 forms from VCl3:<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a>
</p>
VCl3(THF)3 + 3 LiC6H2-2,4,6-Me3 → V(C6H2-2,4,6-Me3)3(THF) + 3 LiCl
<p>This species binds CO and, under appropriate conditions, N2.  <a href="/facts/Trimesitylvanadium/le5LCnj2">V(mesityl)3</a> adds a fourth mesityl group and the resulting "ate complex" can be oxidized to the vanadium(IV) derivative:
</p>
V(mes)3(THF)  + LiMes   → Li[V(mes)4]
Li[V(mes)4]   + air  → V(mes)4(THF)
<p>The tetrakis(norbornyl) complex is also known.
</p><p><a href="/facts/Vanadium_oxytrichloride/I7j4kd7B">Vanadium oxytrichloride</a> is a starting material for organovanadium(IV) and organovanadium(V) compounds:
</p>
VOCl3  + Li(mes)   → Li[VO(mes)3]
Li[VO(mes)3] + <a href="/facts/Chloranil/JoKhpseT">chloranil</a> → VO(mes)3
VOCl3  + ZnPh2   → VOPhCl2  +  "ZnPh(Cl)"
<h2 id="catalysts-and-reagents">Catalysts and reagents</h2>
<p>Well-defined vanadium compounds do not appear as catalysts in any commercial process.<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a>  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 <a href="/facts/Vanadium(III)_acetylacetonate/84jGqQRm">vanadium(III) acetylacetonate</a> with <a href="/facts/Organoaluminium/GM0K5eKE">organoaluminium</a> activators.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a><a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a>
</p>

<h2 id="references">References</h2>

<ol>
<li id="fn:1"><p>Synthesis of Organometallic Compounds: A Practical Guide Sanshiro Komiya Ed. 1997 <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li>
<li id="fn:2"><p>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. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li>
<li id="fn:3"><p>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. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li>
<li id="fn:4"><p>Robert Choukroun, Christian Lorber (2005). "Adventures in Vanadocene Chemistry". Eur. J. Inorg. Chem. 2005 (23): 4683–4692. doi:10.1002/ejic.200500371. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li>
<li id="fn:5"><p>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}}: ISBN / Date incompatibility (help); |journal= ignored (help) <a href="978-0-470-13238-8" target="_blank">978-0-470-13238-8</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li>
<li id="fn:6"><p>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 <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li>
<li id="fn:7"><p>Toshikazu Hirao (1997). "Vanadium in Modern Organic Synthesis". Chemical Reviews. 97 (8): 2707–2724. doi:10.1021/cr960014g. PMID 11851478. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li>
<li id="fn:8"><p>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. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li>
<li id="fn:9"><p>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 978-3-527-30673-2. <a href="978-3-527-30673-2" target="_blank">978-3-527-30673-2</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li>
</ol>

Organovanadium chemistry open-in-new

Organovanadium chemistry