Organolithium complexes, like the organomagnesium Grignard Reagents, are important reactants in organic synthesis. The similarity in structure, bonding, and reactivity of organolithium and -magnesium compounds exemplifies the common chemistry exhibited by representative elements that appear in the same diagonal in the periodic table. Although much debate exists over the degree of covalency within lithium – carbon-bonding interactions, the presence of some covalent character in LiC bonds of alkyllithium compounds is widely accepted. The bonding interactions within organoalkali metal complexes of the heavier alkali metals are generally considered to be strongly electrostatic or ionic in nature. This is supported by a large collection of evidence, consisting primarily of solution NMR data, single-crystal X-ray analyses, and gas-phase computational studies. Many of the organolithium compounds are soluble in hydrocarbons, but organometallic compounds of the heavier group 1 metals generally require more polar solvents. In general, the reactivity of the alkali metals and the reactivity of the organometallic compounds of these metals increase as we go down the group or column. Organoalkali metal compounds are similar to, but more reactive than Grignard reagents. Organoalkali metal compounds are both air- and moisture-sensitive and are sometimes pyrophoric. In addition, organoalkali metal compounds will react as Bronsted bases with protic reagents. Specific details regarding the synthesis, reactivity, and structures of various types of organoalkali metal compounds will be discussed.


Keywords:

alkali;
organoalkali;
lithium;
sodium;
potassium;
rubidium;
cesium;
allyl;
cyclopentadienyl;
alkyl;
aryl;
pentadienyl

Alkali Metals: Organometallic Chemistry

Oligomers of methyllithium and tert-butyllithium (RnLin, n = 1−4; R = Me, t-Bu) as well as phenyllithium (PhnLin, n = 1,4) have been studied by using density functional theory (DFT). Possible confo...

Density Functional Calculations of Methyllithium, t-Butyllithium, and Phenyllithium Oligomers: Effect of Hyperconjugation on Conformation

I. Organoalkali Chemistry

Carbanions appear in many organic or biological reactions as fleeting intermediates, prohibiting direct observation or spectroscopic measurement. An aqueous environment is known to rapidly annihilate a carbanion species, reducing its lifetime to as short as picoseconds. We report that aqueous microdroplets can capture and stabilize reactive carbanion intermediates isolated from four classic organic reactions, aldol and Knoevenagel condensations, alkyne alkylation, and the Reimer-Tiemann reaction, enabling the detection of their carbanion intermediates by desorption electrospray ionization mass spectrometry. This is accomplished in real time of the reaction, allowing new insights into reaction mechanisms to be obtained. The efficacy of microdroplets in capturing such elusive species was examined by varying the solvent and the microdroplet negative charge density. We observed that microdroplets composed of water-methanol outperform other solvents, such as pure water, in capturing carbanions, which is in contrast to the earlier report that presented the highest performance of pure water microdroplets in capturing carbocations. We offer some mechanistic insights to explain the discriminatory behavior of these two oppositely charged species in microdroplets.

Capturing Reactive Carbanions by Microdroplets.

Seventeen aryllithium complexes were studied by 7Li solid-state NMR spectroscopy. The solid structures of most of the complexes studied are known from x-ray crystallography and include differently substituted aryllithium complexes in addition to some phenyllithium complexes. It is shown that the quadrupolar coupling constant, χ, is very sensitive to changes in aggregation and solvation. From the magnitude of χ, it is often possible to deduce the aggregation state and also obtain information about the solvation regarding the number and type of donor atoms coordinating the lithium cation. Copyright © 2000 John Wiley & Sons, Ltd.

7Li Solid-state NMR spectroscopic study of aryllithium complexes: effects of aggregation and solvation

Elucidation et interpretation des spectres de masse des composes suivants: CH 3 Li, n-C 3 H 7 Li, iso-C 3 H 7 Li, n-C 4 H 9 Li, sec-C 4 H 9 Li, iso-C 4 H 9 Li et t-C 4 H 9 Li

Mass spectrometric investigations of alkyllithium compounds in the gas phase

Tetraaquadodeca-μ-halodihalohexaniobium tetrahydrates [(Nb6X12)X2(H2O)4] · 4H2O, X=Cl or Br, were studied using laser desorption/ionization (LDI) Fourier transform ion cyclotron resonance mass spectrometry. Only negative ions were found to form in the gas phase under LDI conditions. The quasimolecular ion, M−=[(Nb6X12)X2]− and the fragment ions, [M−Xnfx100]−, n=1–3, are the highest abundance ions in the LDI mass spectra, indicating the stability of the core cluster, (Nb6X12). Clusters with chlorine atoms as ligands show relatively high affinity for an additional chlorine atom, while clusters with bromine atoms as ligands prefer to lose a bromine atom. The results are compared with those of mass spectra of analogous tantalum clusters.

Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of [(Nb6X12)X2(H2O)4] · 4H2O, X=Cl or Br

Les ionisations de basse energie (6,95 et 8,58 eV) dans les spectres photoelectroniques des tetrameres d'alkyllithium sont interpretes comme des transitions aux etats 2 T et 2 A du cube forme par Li + et C −

Gas−phase electronic structure of alkyllithium compounds

The gas phase of hexanuclear Ta clusters of type [Ta6X12]X2·8H2O, X=Cl, Br was investigated using laser-desorption Fourier-transform mass spectrometry. The [Ta6X12]X ions (m/z=1581 for X=Cl, m/z=2205 for X=Br) are the most characteristic peaks in their negative-ion laser-desorption mass spectra. Additional fragmentations observed are the result of loss of halogen and metal from [Ta6X12]X. Positive ions are observed only in the laser-desorption mass spectra of [Ta6Br12]Br·8H2O.

Laser-desorption Fourier-transform mass spectrometry of [Ta6X12]X2·8H2O, X=C1, Br

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Mass spectrometric investigations of alkyllithium compounds in the gas phase

Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of [(Nb6X12)X2(H2O)4] · 4H2O, X=Cl or Br

Gas−phase electronic structure of alkyllithium compounds

Laser-desorption Fourier-transform mass spectrometry of [Ta6X12]X2·8H2O, X=C1, Br