Title

Charge-Transfer Bonding in Metal–Arene Coordination

Document Type

Article

Language

eng

Publication Date

5-2000

Publisher

Elsevier

Source Publication

Coordination Chemistry Reviews

Source ISSN

0010-8545

Abstract

X-ray crystallographic structures of donor–acceptor complexes of aromatic hydrocarbons with transition metals are re-examined with the focus on the arene ligands. Thus, significant structural and electronic changes are revealed in the arene moiety due to coordination to the metal center including: (i) expansion of the aromatic six-carbon ring; (ii) endocyclic π-bond localization; (iii) distortion of the planarity (folding) of the arene ring; and (iv) shortening of the metal-arene bond distances. All structural features are characteristic of metal–arene (π- or σ-) complexes that exhibit various degrees of (metal-to-ligand) charge transfer. The concept of charge-transfer bonding not only explains the structural details but also the various facets of chemical reactivity of metal-coordinated arenes including efficient carbon-hydrogen bond activation and nucleophilic–electrophilic umpolung, both of which are critical factors in homogeneous metal catalysis.

Comments

Coordination Chemistry Reviews, Vol. 200-202 (May 2000): 831-873. DOI.

Sergey V. Lindeman was affiliated with the University of Houston at the time of publication.

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