<< Chapter < Page Chapter >> Page >


Alkyl lithium compounds are either low melting solids or liquids, and often with high volatility (depending on the substituent) due to the covalent nature of the bonding. They are soluble in aliphatics, aromatics, and ethers. However, while the reaction with ethers is generally slow, [link] , alkyl lithium compounds can polymerize tetrahydrofuran (THF).

Organolithium compounds react rapidly with air and water (both vapor and liquid). The reaction with water is the basis of the Gillman double titration method for determining the concentration of organolithium reagents in solution.


The structure of organolithium compounds is dominated by their highly oligomeric nature as a result of 3-center 2-electron bridging bonds. In all cases the extent of oligomerization is dependant on the identity of the alkyl (or aryl) group. The alkyl-bridged bond is similar to those found for beryllium and aluminum compounds.

In the vapor phase any particular organolithium derivative show a range of oligomeric structures. For example, the mass spectrum of EtLi shows ions associated with both tetramers (e.g., [Et 3 Li 4 ] + ) and hexamers (e.g., [Et 5 Li 6 ] + ). The structures of the different oligomers have been predicted by molecular orbital calculations ( [link] ).

Proposed vapor phase structures for various oligomers of RLi.

Solution molecular weight measurements indicate the oligomerization is present (in the absence of a coordinating ligand such as Et 2 O or an amine). The extent of oligomerization depends on the steric bulk of the alkyl group ( [link] ). Oligomerization and solution structures have also been investigated by 7 Li and 13 C NMR spectroscopy.

Extent of oligomerization (n) for organolithium compounds [RLi] n in benzene solution.
R [RLi] n R [RLi] n
Me 4 Et 6
n Bu 6 t Bu 4

There are a large number of X-ray crystallographically determined structures for organolithium derivatives. The archetypal example is MeLi, which exists as a tetramer in the solid state ( [link] ). The lithium atoms are arranged as a tetrahedron and the carbon atoms are positioned on the center of the facial planes, i.e., the carbon is equidistant from each of the lithium atoms. In contrast, EtLi has a similar tetrahedral structure, but the α-carbon of the ethyl groups are asymmetrically arranged such that it is closer to one lithium atom than the other two.

Solid state structure of MeLi. Copyright: Ben Mills (2007).

It is possible to prepare monomeric organolithium compounds by the addition of amines, especially chelate ligands such as ethylenediamine (en) and tetramethylethylenediamine (TMED). The reactivity of RLi is increased dramatically by the addition of such Lewis bases. For example, PhCH 2 Li shows an increased reactivity of 10 4 with the addition of TMED.

The bonding in organolithium compounds is difficult to describe:

  • Based upon the relative electronegativity of Li (0.98) and C (2.5) it would be expected to have significant ionic character.
  • Organolithium compounds form electron deficient oligomers typical of covalent bonding and clearly not as a result of ionic aggregation.
  • The spin-spin coupling, J (C-Li), observed by NMR spectroscopy (10 – 15 Hz) are consistent with a covalent bond.
  • Organolithium compounds undergo radical reactions.

However, the overall description of the bonding in RLi is that of a covalent interaction with significant polar (ionic) character, i.e., M δ + -C δ - .

The use of organolithium compounds in organic synthesis

Organolithium compounds perform many of the reactions commonly observed for Grignard reagents. However, lithium reagents are generally more reactive than their Grignard analogs.


Organolithium compounds react with water to give the hydrocarbon and lithium hydroxide, [link] . Lithium alkyls also react with other hydroxylic compounds such as alcohols and carboxylic acids, [link] .

One important use of the hydrolysis reaction is specifically deuteration, [link] .

Reaction with carbonyls

Organolithium compounds react with organic carbonyls (aldehydes, ketones, and esters) to yield the alcohol on hydrolysis, [link] . This synthetic route is particularly useful since lithium reagents are far more reactive than the analogous Grignard, allowing reactions to be carried out at lower temperatures and minimizing enolization side reactions.

The high reactivity of alkyl lithium compounds means that they react with carboxylic acids to yield the ketone rather than the lithium carboxylate.

Organolithium compounds generally react with α,β-unsaturated ketones to give the 1,2-addition product, [link] . However, lithium dialkylcuprates, which are formed from the alkyl lithium and copper(I) iodide, [link] , add exclusively by the 1,4-addition, [link] .


One of the most useful methods of preparing organometallic compounds is the exchange reaction of one organometallic compound with a salt of a different metal, [link] . This is an equilibrium process, whose equilibrium constant is defined by the reduction potential of both metals. In general the reaction will proceed so that the more electropositive metal will form the more ionic salt (usually chloride).

Lithium reagents may be used to prepare a wide range of organometallic compounds.


  • G. Graham, S. Richtsmeier, D. A. Dixon. J. Am. Chem. Soc. , 1980, 102 , 5759.
  • E. Weiss, E. A. C. Lucken, J. Organomet. Chem., 1964, 2 , 197.
  • H. O. House, Acc. Chem. Res., 1976, 9 , 59.

Questions & Answers

who was the first nanotechnologist
Lizzy Reply
technologist's thinker father is Richard Feynman but the literature first user scientist Nario Tagunichi.
Norio Taniguchi
I need help
anyone have book of Abdel Salam Hamdy Makhlouf book in pdf Fundamentals of Nanoparticles: Classifications, Synthesis
Naeem Reply
what happen with The nano material on The deep space.?
pedro Reply
It could change the whole space science.
the characteristics of nano materials can be studied by solving which equation?
sibaram Reply
plz answer fast
synthesis of nano materials by chemical reaction taking place in aqueous solvents under high temperature and pressure is call?
hydrothermal synthesis
how can chip be made from sand
Eke Reply
is this allso about nanoscale material
are nano particles real
Missy Reply
Hello, if I study Physics teacher in bachelor, can I study Nanotechnology in master?
Lale Reply
no can't
where is the latest information on a no technology how can I find it
where we get a research paper on Nano chemistry....?
Maira Reply
nanopartical of organic/inorganic / physical chemistry , pdf / thesis / review
what are the products of Nano chemistry?
Maira Reply
There are lots of products of nano chemistry... Like nano coatings.....carbon fiber.. And lots of others..
Even nanotechnology is pretty much all about chemistry... Its the chemistry on quantum or atomic level
no nanotechnology is also a part of physics and maths it requires angle formulas and some pressure regarding concepts
Preparation and Applications of Nanomaterial for Drug Delivery
Hafiz Reply
Application of nanotechnology in medicine
has a lot of application modern world
what is variations in raman spectra for nanomaterials
Jyoti Reply
ya I also want to know the raman spectra
I only see partial conversation and what's the question here!
Crow Reply
what about nanotechnology for water purification
RAW Reply
please someone correct me if I'm wrong but I think one can use nanoparticles, specially silver nanoparticles for water treatment.
yes that's correct
I think
Nasa has use it in the 60's, copper as water purification in the moon travel.
nanocopper obvius
what is the stm
Brian Reply
is there industrial application of fullrenes. What is the method to prepare fullrene on large scale.?
industrial application...? mmm I think on the medical side as drug carrier, but you should go deeper on your research, I may be wrong
STM - Scanning Tunneling Microscope.
how did you get the value of 2000N.What calculations are needed to arrive at it
Smarajit Reply
Privacy Information Security Software Version 1.1a
waht is hydrating power of lithium carbonates
Mahar Reply

Get Jobilize Job Search Mobile App in your pocket Now!

Get it on Google Play Download on the App Store Now

Source:  OpenStax, Chemistry of the main group elements. OpenStax CNX. Aug 20, 2010 Download for free at http://cnx.org/content/col11124/1.25
Google Play and the Google Play logo are trademarks of Google Inc.

Notification Switch

Would you like to follow the 'Chemistry of the main group elements' conversation and receive update notifications?