Cyclopentadienyl complex

Zirconocene dichloride, a cyclopentadienyl complex

A cyclopentadienyl complex is a metal complex with one or more cyclopentadienyl groups (C₅H₅⁻, abbreviated as Cp⁻). Based on the type of bonding between the metals and the cyclopentadienyl]] moieties, cyclopentadienyl complexes are classified into the following three categories: a) π-complexes, b) σ-complexes, and c) ionic complexes.

Cyclopentadienyl ligand

The alkali-metal cyclopentadienyl complexes react with various transition metal compounds to form a variety of complexes that are throughout chemistry. The Cp ligand typically bonds to metals through all five carbon atoms, like in ferrocene, [FeCp₂]; chromocene, [CrCp₂]; cobaltocene, [CoCp₂]; and nickelocene, [NiCp₂]. When the Cp rings are mutually parallel the compound is known as a sandwich complex. This area of organometallic chemistry was first discovered in 1954 with the realization of the structure of ferrocene.^[1] Some metallocenes, notably rhodocene, [RhCp₂], and nickelocene, do exist in some forms where the metal-to-ring binding does not include all five ring atoms.

Other metals form bent structures, such as zirconocene dichloride, [ZrCp₂Cl₂], which is a catalyst for ethylene polymerization.

Bonding of Cp-ligands

Cp-ligands are generally bound via all 5 carbon atoms to a metal centre (η⁵-coordination π-complexes). In rare cases, the Cp unit can bond through three carbon atoms, like in [(η³-Cp)WCp(CO)₂]; or through one carbon atom, as in [(η¹-Cp)FeCp(CO)₂].

π-complexes

Metals and cyclopentadienyl moieties connected by π-bonds are called π-complexes. π-Complexes, especially in the η⁵-type coordination mode, are the most typical of the three types of complexes. Almost all of the transition metals, that is, group 4 to 10 metals, employ this coordination mode. η³-type π-complexes are also seen, depending on the electronic configuration of the metal centre. In this mode, three atoms are bonded to the metal as an allyl-anion ligand, and the remaining two of the Cp are more like a simple alkene.

σ-complexes

σ-Complexes have a direct σ-bond between the metal and one of the carbons of the cyclopentadienyl group. Typical examples of this type of complex are group 14 metal complexes such as CpSiMe₃, Cp₂Sn, and CpPb. CpSiMe₃ is commonly used as the starting material for the synthesis of group 4 metal cyclopentadienyl complexes.

Ionic complexes

Ionic complexes primarily involve alkali metal cations and alkali earth metals cations connected to cyclopentadienyl anions. These complexes are not ionic, but the bonding is probably highly polar and often η-1 bonding is indicated. Ionic type complexes are generally synthesized directly by reaction of cyclopentadiene and the metal in a non-aromatic solvent. These complexes can be good starting materials for several π-type cyclopentadienyl complexes.

Synthesis of Cp complexes

Most cyclopentadienyl complexes are prepared by treating a metal halide with sodium cyclopentadienide (NaCp). For the preparation of some particularly robust complexes, cyclopentadiene is employed in the presence of a conventional base such as NaOH. Specialized alternatives to NaCp include trimethylsilyl cyclopentadiene (CpSiMe₃) and thallium cyclopentadienide (CpTl) in an ethereal solvent. Most Cp complexes have various other ligands besides a cyclopentadienyl ligand, such as carbonyl, halogen, alkyl, and so on. Biscyclopentadienyl complexes are called metallocenes. It is often the case that these complexes are thermally stable, and they are used for various catalysts. For example, some of the early transition metal complexes, such as Cp₂TiCl₂ and Cp₂ZrCl₂ with aluminoxane as a co-catalyst, can catalyze olefin polymerization. Such species are called Kaminsky-type catalysts.

Comparison Cp* with Cp

Cp-metals and color
Compound	Cp	Cp*
Cp2Fe	yellow	yellow
CpTiCl3	yellow	red
[Cp*Fe(CO)2]2		red-violet
[Cp*RhCl2]2		red
Cp*Re(CO)3		colorless
Cp*Mo(CO)2CH3		orange
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references

The pentamethylcyclopentadienyl ligand (Cp*) is an important ligand in organometallic compounds arising from the binding of the five ring-carbon atoms in C₅Me₅⁻, or Cp*⁻, to metals. Relative to the more common cyclopentadiene (Cp) ligand, Cp* offers certain features that are often advantageous. Being more electron-rich, Cp* is a stronger donor and is less easily removed from the metal. Consequently its complexes exhibit increased thermal stability. Its steric bulk allows the isolation of complexes with fragile ligands. Its bulk also attenuates intermolecular interactions, decreasing the tendency to form polymeric structures. Its complexes also tend to be highly soluble in non-polar solvents.

Synthesis of Cp* complexes

Some representative reactions leading to such Cp*-metal complexes include

Cp*H + C₄H₉Li → Cp*Li + C₄H₁₀

2 Cp*Li + TiCl₄ → Cp*₂TiCl₂ + 2 LiCl

Cp*₂TiCl₂ + TiCl₄ → 2 Cp*TiCl₃

Cp*Li + Me₃SiCl → Cp*SiMe₃ + LiCl

Cp*SiMe₃ + TiCl₄ → Cp*TiCl₃ + Me₃SiCl

2 Cp*H + 2 Fe(CO)₅ → [Cp*Fe(CO)₂]₂ + H₂

Some Cp* complexes are prepared using hexamethyl Dewar benzene as the precursor. This method was traditionally used for [Rh(C₅Me₅)Cl₂]₂.

References

1. ^ Crabtree, R. H. (2001). The Organometallic Chemistry of the Transition Metals (3rd Edn.) New York: John Wiley and Sons.
2. ^ Shriver, D.; Atkins, P. (1999). Inorganic Chemistry, New York: W. H. Freeman.
3. Yamamoto, A. Organotransition Metal Chemistry: Fundamental Concepts and Applications. (1986) p. 105
4. Overview of Cp* Compounds: Elschenbroich, C. and Salzer, A. Organometallics: a Concise Introduction (1989) p. 47
5. Initial examples of the synthesis of Cp*-metal complexes: R. B. King, M. B. Bisnette, Journal of Organometallic Chemistry volume, 8 (1967) pp. 287-297.