Heavier Group 2 Grignard Reagents of the Type Aryl-Ae(L)n-X (Post-Grignard Reagents)

  • Matthias Westerhausen
  • Jens Langer
  • Sven Krieck
  • Reinald Fischer
  • Helmar Görls
  • Mathias Köhler
Chapter
First Online:
Part of the Topics in Organometallic Chemistry book series (TOPORGAN, volume 45)

Abstract

Whereas hitherto no general procedure has been developed for the synthesis of alkylcalcium halides, arylcalcium halides were found to be easily accessible post-Grignard reagents. The large discrepancy between the inertness of metallic calcium and the organocalcium derivatives requires an activation of the metal prior to use. The arylcalcium compounds can be obtained in large yields from iodoarenes and in smaller yields from bromoarenes. Chloro- and fluoroarenes represent no suitable substrates for the direct synthesis with calcium. Diverse substituents and functional groups are tolerated in para and meta position, whereas in ortho position the tolerance of functional groups is reduced. Only the para-phenyl substituted arylcalcium derivatives are destabilized and instantaneously undergo degradation reactions. These arylcalcium complexes commonly crystallize with six-coordinate calcium centers in distorted octahedral environments. Bulky substituents allow the preparation of organometallics with smaller coordination numbers whereas the use of multidentate ethers with small bites (intraligand O···O distance) leads to compounds with seven- or eight-coordinate calcium atoms. The arylcalcium halides show spectroscopic properties and reactivities more similar to organolithium compounds than to classic Grignard reagents. Reduction of iodoarenes is also possible with strontium and barium, but these homologous reagents are more reactive than the calcium derivatives enhancing the tendency to cleave solvent molecules. The objective of this review includes the credo that arylcalcium halides and pseudohalides are valuable synthons in organometallic chemistry which can be at least as valuable as organolithium reagents due to their ease of preparation and manageability on the one hand and their high and tunable reactivity on the other.

Graphical Abstract

Keywords

Arylcalcium Calcium Diarylcalcium Ether degradation Organylcalcium Post-grignard reagents 

List of Abbreviations

Ae

Alkaline-earth metal

Ar

Aryl

Bu

Butyl

18-crown-6

1,4,7,10,13,16,-Hexaoxacyclooctadecane

Cp

Cyclopentadienyl

Diglyme

Diethylene glycol dimethyl ether

Diox

1,4-Dioxane

DME

1,2-Dimethoxyethane

e−

Electron

Et

Ethyl

HMTETA

N,N,N′,N″,N″′,N″′-Hexamethyltriethylenetetramine

L

Ligand

M

Metal

Me

Methyl

Mes

2,4,6-Trimetylphenyl

Naph

Naphthyl

Ph

Phenyl

Pr

Propyl

R

Substituent

Solv

Solvent

THF

Tetrahydrofuran

THP

Tetrahydropyran

Tipp

2,4,6-Tri-isopropylphenyl

TMEDA

N,N,N′,N′-Tetramethylethylenediamine

Tol

4-Methylphenyl

TMTN

N,N′,N″-Trimethyl-1,4,7-triazacyclononane

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Notes

Acknowledgements

We thank the German Research Foundation (Deutsche Forschungsgemeinschaft, DFG, Bonn-Bad Godesberg) and the Verband der Chemischen Industrie (VCI/FCI, Germany) for generous financial support and Ph.D. grants. In addition, this review is based on numerous results of former skillful and enthusiastic coworkers who expedited this field of post-alkaline-earth metal chemistry. We are also very grateful to the research group of Prof. Markus Reiher (ETH Zurich, Switzerland) for supporting us with quantum chemical calculations in order to clarify reaction mechanisms and molecular structures and to evaluate bonding situations of post-Grignard reagents and subvalent s-block compounds. Furthermore, we like to thank Prof. Karin Ruhlandt-Senge (Syracuse University, NY/USA) for valuable discussions during her stays in Jena.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  • Matthias Westerhausen
    • 1
  • Jens Langer
    • 1
  • Sven Krieck
    • 1
  • Reinald Fischer
    • 1
  • Helmar Görls
    • 1
  • Mathias Köhler
    • 1
  1. 1.Institute of Inorganic and Analytical ChemistryFriedrich Schiller University of JenaJenaGermany

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