Phenyllithium

<h2 id="preparation">Preparation</h2>
Phenyllithium was first produced by the reaction of lithium metal with <a href="/facts/Diphenylmercury/2UKpgUoU">diphenylmercury</a>:<a class="footnote-ref" id="fnref:3" href="#fn:3">3</a>

(C6Η5)2Ηg + 2 Li → 2 C6Η5Li + Ηg
Reaction of a phenyl halide with lithium metal produces phenyllithium:

Ph−X + 2 Li → Ph−Li + LiX
Phenyllithium can also be synthesized with a metal-halogen exchange reaction:

n-BuLi + Ph−X → n-BuX + Ph−Li
The predominant method of producing phenyllithium today are the latter two syntheses.

<h2 id="reactions">Reactions</h2>
The primary use of PhLi is to facilitate formation of carbon-carbon bonds by nucleophilic addition and substitution reactions:

PhLi + R2C=O → PhR2CO−Li+
<a href="/facts/2-Phenylpyridine/nV6MFC30">2-Phenylpyridine</a> is prepared by the reaction of phenyl lithium with pyridine, a process that entails an addition-elimination pathway:<a class="footnote-ref" id="fnref:4" href="#fn:4">4</a>

C6H5Li + C5H5N → C6H5−C5H4N + LiH
<h2 id="structure-and-properties">Structure and properties</h2>

Phenyllithium is an <a href="/facts/Organolithium/xgYnjhP3">organolithium</a> compound that forms monoclinic crystals. Solid phenyllithium can be described as consisting of dimeric Li2Ph2 subunits. The Li atoms and the <a href="/facts/Arene_substitution_pattern/ByM7Y1b9">ipso</a> carbons of the phenyl rings form a planar four-membered ring. The plane of the phenyl groups are perpendicular to the plane of this Li2C2 ring. Additional strong intermolecular bonding occurs between these phenyllithium dimers and the π-electrons of the phenyl groups in the adjacent dimers, resulting in an infinite polymeric ladder structure.<a class="footnote-ref" id="fnref:5" href="#fn:5">5</a>

In solution, it takes a variety of structures dependent on the organic solvent. In <a href="/facts/Tetrahydrofuran/P5t6SkMK">tetrahydrofuran</a>, it equilibrates between monomer and dimer states. In ether, as it is commonly sold, phenyllithium exists as a tetramer. Four Li atoms and four ipso carbon centers occupy alternating vertices of a distorted cube. Phenyl groups are at the faces of the tetrahedron and bind to three of the nearest Li atoms.
The C–Li bond lengths are an average of 2.33 Å. An ether molecule binds to each of the Li sites through its oxygen atom. In the presence of LiBr, a byproduct of directly reacting lithium with a phenyl halide, the [(PhLi·Et2O)4] complex instead becomes [(PhLi·Et2O)3·LiBr]. The Li atom of LiBr occupies one of the lithium sites in the <a href="/facts/Cubane-type_cluster/oDGLa2Fk">cubane-type cluster</a> and Br atom sits in an adjacent carbon site.<a class="footnote-ref" id="fnref:6" href="#fn:6">6</a>

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

<ol>
<li id="fn:1">Wietelmann, U.; Bauer, R. J. "Lithium and Lithium Compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a15_393. ISBN 978-3-527-30673-2. <a href="978-3-527-30673-2" target="_blank">978-3-527-30673-2</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></li>
<li id="fn:2">Gilman, H.; Zoellner, E. A.; Selby, W. M. (1932). "An Improved Procedure for the Preparation of Organolithium Compounds". Journal of the American Chemical Society. 54 (5): 1957–1962. doi:10.1021/ja01344a033. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></li>
<li id="fn:3">Green, D. P.; Zuev, D. (2008). "Phenyllithium". Encyclopedia of Reagents for Organic Synthesis. Wiley and Sons. doi:10.1002/047084289X.rp076.pub2. ISBN 978-0471936237. <a href="978-0471936237" target="_blank">978-0471936237</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></li>
<li id="fn:4">Evans, J. C. W.; Allen, C. F. H. "2-Phenylpyridine" Organic Syntheses (1938), vol. 18, p. 70 doi:10.15227/orgsyn.018.0070 <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></li>
<li id="fn:5">Dinnebier, R. E.; Behrens, U.; Olbrich, F. (1998). "Lewis Base-Free Phenyllithium: Determination of the Solid-State Structure by Synchrotron Powder Diffraction". Journal of the American Chemical Society. 120 (7): 1430–1433. doi:10.1021/ja972816e. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></li>
<li id="fn:6">Hope, H.; Power, P. P. (1983). "Isolation and Crystal Structures of the Halide-Free and Halide-Rich Phenyllithium Etherate Complexes [(PhLi•Et2O)4] and [(PhLi•Et2O)3•LiBr]". Journal of the American Chemical Society. 105 (16): 5320–5324. doi:10.1021/ja00354a022. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></li>
</ol>

Phenyllithium open-in-new

Phenyllithium