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General chemical structure of a Metallocene compound, where M is a metal cation

A metallocene is a compound typically consisting of two cyclopentadienyl anions (Cp, which is C₅H₅^-) bound to a metal center (M) in the oxidation state II, with the resulting general formula (C₅H₅)₂M. Closely related to the metallocenes are the metallocene derivatives, e.g. titanocene dichloride, vanadocene dichloride. Certain metallocenes and their derivatives exhibit catalytic properties, although metallocenes are rarely used industrially. Cationic group 4 metallocene derivatives related to [Cp₂ZrCH₃]⁺ catalyze olefin polymerization. Metallocenes are a subset of a broader class of organometallic compounds called sandwich compounds.

In the structure shown at right, the two pentagons are the cyclopentadienyl anions with circles inside them indicating they are aromatically stabilized. Here they are shown in a staggered conformation.

History

Ferrocene

The first metallocene to be classified was ferrocene, and was discovered simultaneously in 1951 by Kealy and Pauson, and Miller et al. Kealy and Pauson were attempting to synthesize fulvalene through the oxidation of a cyclopentadienyl Grignard reagent with anhydrous FeCl₃ when they dicovered C₁₀H₁₀Fe as their product. At the same time, Miller et al reported the same iron product from a reaction of cyclopentadiene with iron in the presence of alumninum, potassium, or molybdenum oxides. The structure was determined by Wilkinson and Fischer and they were awarded in Nobel Prize for Chemistry in 1973 for the structural determination of Fe(C₅H₅)₂. They determined that the carbon atoms of the cyclopentadienyl (Cp) ligand contributed equally to the bonding and that bonding occured due to the metal d-orbitals and the π-electrons in the p-orbitals of the Cp ligands. This complex is now known as ferrocene and the group of transition metal dicyclopentadienyl compounds is known as metallocenes and have the general formula [(η⁵-C₅H₅)₂M]. Fischer et al. first prepared the ferrocene derivitaves involving Co and Ni.

Definition

Ball-and-stick model of a metallocene molecule where the cyclopentadienyl anions are in a staggered conformation. The purple ball in the middle represents the metal cation.

The general name metallocene is derived from ferrocene, (C₅H₅)₂Fe or Cp₂Fe , systematically named bis(η⁵-cyclopentadienyl)iron(II). According to the IUPAC definition, a metallocene contains a transition metal and two cyclopentadienyl ligands coordinated in a sandwich structure, i. e., the two cyclopentadienyl anions are co-planar with equal bond lengths and strengths. Using the nomenclature of "hapticity", the equivalent bonding of all 5 carbon atoms of a cyclopentadienyl ring is denoted as η⁵, pronounced "pentahapto." There are exceptions, such as uranocene, which has two cyclooctatetraene rings sandwiching a uranium atom.

In metallocene names, the prefix before the -ocene ending indicates what metallic element is between the Cp groups. For example in ferrocene, iron(II), ferrous iron is present.

In contrast to the more strict definition proposed by IUPAC, which requires a d-block metal and a sandwich structure, the term metallocene and thus the denotation -ocene, is applied in the chemical literature also to non-transition metal compounds, such as Cp₂Ba, or structures where the aromatic rings are not co-planar, such as found in manganocene or titanocene dichloride (Cp₂TiCl₂).

Some metallocene complexes of actinides have been reported where there are three cyclopendadienyl ligands for a monometallic complex, all three of them bound η⁵.

Classification

Nickel triple decker sandwich complex

There are many (η-C₅H₅)-metal complexes and they can be classified by the following formulas:

Formula	Description
[(η-C5H5)2M]	Symmetrical, classical 'sandwich' structure
[(η-C5H5)2MLx]	Bent or tilted Cp rings with additional ligands, L
[(η-C5H5)MLx]	Only one Cp ligand with additional ligands, L

Metallocene complexes can also be classified by type:

1. Parallel
2. Multidecker
3. Half-sandwich
4. Bent or tilted
5. More than two Cp ligands

Synthesis of Metallocenes

Main article: Sandwich compound

There are three main routes that are normally employed in the formation of these types of compounds:

1. Using a metal salt and cyclopentadienyl reagents

The starting point is the cracking of dicyclopentadienyl.

Working in a weak acidic environment, cyclopentadienyl can be deprotonated by strong bases or alkali metals. Na (Cp) is the preferred reagent for this type of reactions.

MCl₂ + 2NaC₅H₅ → (C₅H₅)₂M (M= V, Cr, Mn, Fe, Co; Solvent= THF, DME, NH3)

CrCl₃ + 3NaC₅H₅→ [(C₅H₅)₂Cr] + ½ C₁₀H₁₀+ 3NaCl

NaCp acts as a reducing agent and forms cyclopentadienyl metal. Depending on the reaction condition it can form complexes containing σ- bonded cyclopentadienyl rings when added to metal salts.

2. Using a metal and cyclopentadiene

This technique provides synthetic advantages of using metal atoms in the vapor phase rather than the solid metal. The highly reactive atoms or molecules are generated at high temperature under vacuum and the brought together with chosen reactants on a cold surface.

M + CH₆ → MC₅H₅ + ½ H₂ (M= Li, Na, K)

M + 2CH₆ → [(C₅H₅)₂M] + H₂ (M= Mg, Fe)

3. Using a metal salt and cyclopentadiene

If the metal salt has poor basicity it is not able to deprotonate cyclopentadiene, a strong base can be used to produce cyclopentadienyl anions in situ.

Tl₂SO₄ + 2C₅H₆ + 2OH^- →2TlC₅H₅ + 2H₂O+ SO₄^-2

Many other methods have been developed. Chromocene can be prepared from chromium hexacarbonyl by direct reaction with cyclopentadiene in the presence of diethylamine; in this case, the formal deprotonation of the cyclopentadiene is followed by reduction of the resulting protons to hydrogen gas, facilitating the oxidation of the metal centre.

Cr(CO)₆ + 2C₅H₆ → Cr(C₅H₅)₂ + 6CO + H₂

Metallocenes generally have high thermal stability. Ferrocene can be sublimed in air at over 100 °C with no decomposition; metallocenes are generally purified by vacuum sublimation. Charge-neutral metallocenes are soluble in common organic solvents. Alkyl substituted derivative are particularly soluble, even in alkane solvents.

Structure

A structural trend for the series MCp₂ involves the variation of the M-C bonds, which elongate as the valence electron count deviates from 18.

M(C5H5)2	rM-C (pm)	valence electron count
Fe	203.3	18
Co	209.6	19
Cr	215.1	16
Ni	218.5	20
V	226	15

In metallocenes of the type (C₅R₅)₂M, the cyclopentadienyl rings rotate with very low barriers. Single crystal X-ray diffraction studies reveal both eclipsed or staggered rotamers. For non-substituted metallocenes the energy difference between the staggered and eclipsed conformations is only a few kJ/mol. Crystals of ferrocene and osmocene exhibit eclipsed conformations at low temperatures, whereas in the related bis(pentamethylcyclopentadienyl) complexes the rings usually crystallize in a staggered conformation, apparently to minimize steric hindrance between the methyl groups.

Spectroscopic Properties

Spectroscopic properties:

1. Vibrational (infrared and raman) spectroscopy of metallocenes.

Infrared and Raman spectroscopies have proved to be important in the analysis of cyclic polyenyl metal sandwich species with particular use in elucidating covalent or ionic M-ring bonds and distinguishing between centrally and coordinated rings. Some typical spectral bands and assignments of iron group metallocenes are shown in the following table:

	Ferrocene (cm-1)	Ruthenocene (cm-1)	Osmocene (cm-1)
C-H stretch	3085	3100	3095
C-C stretch	1411	1413	1405
Ring deformation	1108	1103	1096
C-H deformation	1002	1002	995
C-H out-of-plane bend	811	806	819
Ring tilt	492	528	428
M-ring stretch	478	446	353
M-ring bend	170	185	-

2. NMR (¹H and ¹³C) spectroscopy of metallocenes.

Nuclear magnetic resonance is the most applied tool in the study of metal sandwich compounds and organometallice species, giving information on nuclear structures in solution, as liquids, gases, and in the solid state. ¹H NMR chemical shifts for diamagnetic organotransition metal compounds is usually observed between 25- -40 ppm, but this range is much more narrow for diamagnetic metallocene complexes, with chemical shifts usually observed between 7-3 ppm.

3. Mass spectrometry of metallocenes.

Mass spectrometry of metallocene complexes has been very well studied and the effect of the metal on the fragmentation of the organic moiety has received considerable attention and the identification of metal-containing fragments is often facilitating by the isotope pattern of the metal. The three major fragments observed in mass spectrometry are the molecular ion peak [C₁₀H₁₀M]⁺ and the fragment ions, [C₅H₅M]⁺ and M⁺.

Derivatives

Main article: Sandwich compound

Derivatives of Metallocenes:

After the discovery of ferrocene, the synthesis and characterization of derivatives of metallocene and other sandwich compounds attracted researchers’ interests.

1. Metallocenophanes

Metallocenophanes are feature linking of the cyclopentadienyl or polyarenyl rings by the introduction of a heteroannular bridge (bridges). These compounds have been found to undergo thermal ring-opening polymerizations (ROP) which are example of high molecular mass, soluble polymers with transition metals in the main polymer chian and they can exhibit unusual physical and chemical properties. *Ansa-metallocenes are derivatives of metallocenes include structures with an intramolecular bridge between the two cyclopentadienyl rings (ansa-metallocenes)

2. Polynuclear and heterobimetallic metallocenes

Ferrocene derivatives: Biferrocenophanes have been studied for their mixed valance properties. Upon one-electron oxidation of a compound with two or more equivalent ferrocene moieties the electron vacancy could be localized on one ferrocene unit or completely delocalized.

Ruthenocene derivatives: In the solid state biruthenocene is disordered and adopts the transoid conformation with the mutual orientation of Cp rings depending on the intermolecular interactions.

Vanadocene and rhodocene derivatives: Vanadocene complexes have been used as starting materials for the synthesis of heterobimetallic complexes. The 18 Valence electron ions [CpRh]⁺ are very stable, unlike the neutral monomers Cp₂Rh which dimerise immediately at room temperature and they have been observed in matrix isolation.

3. Multi-Decker sandwich compounds

These types of materials are important for use as building block for creating materials with useful electronic properties. The first triple-decker sandwich compound featuring cyclopentadienyl ligands was formed in 1972. Triple decker complexes are composed of three Cp anions and two metal cations in alternating order, e.g. [Ni₂Cp₃]⁺.

4. Metallocenium cations

The most famous example is ferrocenium, [Fe(C₅H₅)₂]⁺, derived from oxidation of ferrocene (few metallocene anions are known).

Uses and Importances

Olefin polymerization using metallocene catalysts has improved upon the traditional Ziegler–Natta catalysis by introducing polymer tacticity and increasing productivity.

The ferrocene/ferrocenium biosensor is used as a glucose sensor and determines the levels of glucose in a sample electrochemically through a series of connected redox cycles.

A group of bent metallocene dihalides [Cp₂MX₂] have shown anti tumor properties for M=Ti, Mo, Nb.

Ferrocene exhibits flame-retardant and smoke suppressing properties for polymeric materials such as poly(vinylchloride).

See also

• Jemmis mno rules

Additional references

1. A. Salzer (1999). "Nomenclature of Organometallic Compounds of the Transition Elements". Pure Appl. Chem. 71 (8): 1557–1585. doi:10.1351/pac199971081557. S2CID 14367196.
2. Robert H. Crabtree The Organometallic Chemistry of the Transition Metals 4th ed. Wiley-Interscience: 2005.
3. Miessler, Gary L. (2004). Inorganic Chemistry. Upper Saddle River, New Jersey: Pearson Education, Inc. Pearson Prentice Hall. ISBN 0-13-035471-6. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
4. F.A.Cotton and G.Wilkinson, “Inorganic Chemistry”, 5th edn, Wiley 1988, pp. 626–7