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Cationic (η6-arene)- and Neutral (η5-cyclohexadienyl)-tricarbonylmanganese Complexes: Synthesis and Reactivity

Organomanganese Compounds (2011)

  1. Françoise Rose-Munch,
  2. Eric Rose,
  3. Antoine Eloi

Published Online: 15 SEP 2010

DOI: 10.1002/9780470682531.pat0538

Patai's Chemistry of Functional Groups

Patai's Chemistry of Functional Groups

How to Cite

Rose-Munch, F., Rose, E. and Eloi, A. 2010. Cationic (η6-arene)- and Neutral (η5-cyclohexadienyl)-tricarbonylmanganese Complexes: Synthesis and Reactivity. Patai's Chemistry of Functional Groups. .

Author Information

  1. Université Pierre et Marie Curie, UPMC Paris 6, IPCM, UMR CNRS 7201, Laboratoire de Chimie Organique et Organométallique, Case 181, Paris Cedex 05, France

Publication History

  1. Published Online: 15 SEP 2010

Chemistry Terms

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The tricarbonyl-chromium and -manganese groups are known to easily coordinate arene rings to form η6-arene complexes. The electrophilic nature of the tricarbonyl metal fragments makes the arene electron-deficient and renders it susceptible to nucleophilic attack. It is for these reasons that a new trend has emerged, the study of the chemistry of (η5-cyclohexadienyl)Mn(CO)3 complexes which are easily obtained by addition of a nucleophile to the arene ring. In the last ten years, the discovery of new methods of functionalization involving Pd cross-coupling and lithiation reactions has greatly expanded the scope of the (η5-cyclohexadienyl)Mn(CO)3 complexes and consequently represents a key step in the development of the arene manganese chemistry since [(η6-arene)Mn(CO)3]+ complexes can be easily obtained by rearomatization of the corresponding (η5-cyclohexadienyl)Mn derivatives. The present review aims to describe the situation for the synthesis and the reactivity of η6-arene-Mn complexes as well as that of η5-cyclohexadienyl-Mn complexes to highlight the recent breakthrough in their chemistry. The main reactivities described for η5 Mn complexes correspond to nucleophilic addition, lithiation/electrophilic quench, lithium/halogen exchange and Pd catalyzed reactions. These types of reactions can be efficiently compared with those well studied in η6 arenetricarbonylchromium complexes. All these recent developments in the functionalization of η5- and η6-Mn complexes described in this chapter clearly open a revival period for this type of complexes which are starting to emerge as a valuable and versatile class of compounds more environmentally friendly than their Cr analogs.


  • 6-Arene)tricarbonylmanganese Complexes;
  • 6-Arene)tricarbonylchromium Complexes;
  • Acidity of the benzylic protons;
  • 5-Cyclohexadienyl)tricarbonylmanganese Complexes;
  • (Arene)tricarbonylmanganese Complexes;
  • (Arene)tricarbonylchromium Complexes;
  • Cyclohexenones;
  • Nucleophilic addition;
  • Agostic bond;
  • Cine and tele nucleophilic substitutions;
  • Pd catalyzed reactions;
  • Lithiation;
  • Rearomatization;
  • Planar chiral manganese complexes;
  • Conformation