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Coordination Chemistry Reviews
Volume 250, Issues 9-10, May 2006, Pages 1032-1055
Recent Developments in Organometallic Chemistry: 2006
 
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doi:10.1016/j.ccr.2005.11.001    How to Cite or Link Using DOI (Opens New Window)
Copyright © 2005 Elsevier B.V. All rights reserved.

Review

Perfluoroaryl-substituted cyclopentadienyl complexes of transition metals

Paul A. DeckCorresponding Author Contact Information, E-mail The Corresponding Author

Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA

Received 28 September 2005. 
Available online 19 January 2006.

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Abstract

A review with 172 references. Cyclopentadienyl (Cp) and its substituted congeners are among the most common ligands in organometallic chemistry. Ring substituents attached to Cp can influence the structure, physico-chemical properties, and reactivity of coordinated metal fragments. This article describes the synthesis of perfluoroaryl-substituted cyclopentadienes and indenes and their use as transition metal ligands. Emphasis is placed on trends in spectroscopic and electrochemical behavior, structure, and reactivity that arise from the highly electron-withdrawing character of the perfluoroaryl substituents.

Keywords: CF activation; Cyclopentadienyl; Electronic effects; Metallocene; Pentafluorophenyl

Abbreviations: Cp, cyclopentadienyl; Cp*, pentamethylcyclopentadienyl; CpCF3, (trifluoromethyl)cyclopentadienyl; C6F5Cp, (pentafluorophenyl)cyclopentadienyl

Article Outline

1. Introduction
1.1. Substituent effects
1.2. Steric effects
1.3. Electronic substituent effects
1.3.1. Problems with electron-withdrawing substituents
1.3.2. Alternative strategies for working with reactive substituents
1.4. Why perfluoroaryl substituents?
2. Ligand synthesis
2.1. Cyclopentadienes bearing pentafluorophenyl substituents
2.1.1. Early syntheses
2.1.2. Synthesis by nucleophilic aromatic substitution
2.1.3. Cyclopentadienes bearing pentafluorophenyl and tert-butyl substituents
2.2. Cyclopentadienes bearing perfluoro-4-tolyl substituents
2.3. Cyclopentadienes bearing perfluoro-4-pyridyl substituents
2.4. Pentafluorophenyl-substituted indenes and fluorenes
2.5. Cyclopentadienes bridged by the perfluoro-4,4′-biphenylene moiety
2.6. Cyclopentadienes bearing partially fluorinated aryl substituents
2.7. Structural highlights
3. Synthesis of transition metal complexes bearing perfluoroaryl substituents
3.1. Titanium, zirconium, and hafnium complexes
3.2. Molybdenum and tungsten complexes
3.3. Manganese and rhenium complexes
3.4. Iron and cobalt complexes
3.4.1. Arylation of lithioferrocenes
3.4.2. Synthesis from perfluoroaryl-substituted cyclopentadienyl anions
4. Structure and dynamics
4.1. General structural features
4.2. Arene stacking
4.3. Conformational properties
4.3.1. Cp-aryl torsional angles
4.3.2. Axial conformations of parallel metallocene
5. Physicochemical analyses of perfluoroaryl substituent effects
5.1. Infared spectroscopy
5.2. Solution voltammetry
6. Reactions of perfluoroaryl-substituted cyclopentadienylmetal complexes
6.1. Nucleophilic aromatic substitution
6.2. C–F ortho-activation
6.3. Wedge ligand substitution and abstraction in group 4 metallocene complexes
6.4. Olefin polymerization catalyzed by group 4 metallocene complexes
7. Closing remarks
References