![DIPNIP](https://upload.wikimedia.org/wikipedia/commons/4/43/DIPNIP.png)
In
organometallic chemistry
Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and so ...
, metallacyclopentanes are compounds with the formula L
nM(CH
2)
4 (L
n =
ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electr ...
s, and M = metal). They are a type of
metallacycle
In organometallic chemistry, a metallacycle is a derivative of a carbocyclic compound wherein a metal has replaced at least one carbon center; this is to some extent similar to heterocycles. Metallacycles appear frequently as reactive intermediates ...
. Metallacyclopentanes are intermediates in some metal-catalysed reactions in
homogeneous catalysis
In chemistry, homogeneous catalysis is catalysis by a soluble catalyst in a solution. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysis ...
.
Synthesis
Traditionally, metallacyclopentanes are prepared by dialkylation of metal dihalides with 1,4‐bis(bromomagnesio)butane or the related dilithio reagent. The complex Ni(
bipyridine Bipyridines also known as bipyridyls, dipyridyls, and dipyridines, are a family of chemical compounds with the formula (C5H4N)2, consisting of two pyridyl (C5H4N) rings. Pyridine is an aromatic nitrogen-containing heterocycle. Bipyridines are of sig ...
)C
4H
8 is prepared by oxidative addition of 1,4-dibromobutane to Ni(0) precursors.
[ Metallacyclopentanes also arise via the dimerization of ethylene within the coordination sphere of a low-valence metal center. This reaction is relevant to the catalytic production of butenes and related alkenes.
]
Structure
Unsubstituted metallacyclopentanes adopt conformations related to cyclopentane itself: open-envelope conformation and a twisted open-envelope structure.
Occurrence
Early examples of metallacyclopentanes come from studies of the Ni-catalyzed linear- and cyclo-dimerization of ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
s. Linear dimerization proceeds via beta-hydride elimination of the nickelacyclopentane (Ph3P)Ni(CH2)4 whereas cyclodimerization to give cyclobutane
Cyclobutane is a cycloalkane and organic compound with the formula (CH2)4. Cyclobutane is a colourless gas and commercially available as a liquefied gas. Derivatives of cyclobutane are called cyclobutanes. Cyclobutane itself is of no commercial ...
proceeds by reductive elimination from the related (Ph3P)2Ni(CH2)4. Another example of a metallacyclopentane is the titanocene derivative Cp2Ti(CH2)4.
Metallacyclopentanes are intermediates in the metal-catalysed dimerization
A dimer () (''wikt:di-, di-'', "two" + ''-mer'', "parts") is an oligomer consisting of two monomers joined by bonds that can be either strong or weak, Covalent bond, covalent or Intermolecular force, intermolecular. Dimers also have significant im ...
, trimerization
In chemistry, a trimer (; ) is a molecule or polyatomic anion formed by combination or association of three molecules or ions of the same substance. In technical jargon, a trimer is a kind of oligomer derived from three identical precursors ofte ...
, and tetramerization of ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene i ...
to give 1-butene
1-Butene (or 1-Butylene) is the organic compound with the formula CH3CH2CH=CH2. It is a colorless gas that is easily condensed to give a colorless liquid. It is classified as a linear alpha-olefin. It is one of the isomers of butene (butylene). I ...
, 1-hexene, and 1-octene
1-Octene is an organic compound with a formula CH2CHC6H13. The alkene is classified as a higher olefin and alpha-olefin, meaning that the double bond is located at the alpha (primary) position, endowing this compound with higher reactivity and thu ...
, respectively. These compounds are of commercial interest as comonomer In polymer chemistry, a comonomer refers to a polymerizable precursor to a copolymer aside from the principal monomer. In some cases, only small amounts of a comonomer are employed, in other cases substantial amounts of comonomers are used. Furthe ...
s, used in the production of polyethylene
Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging ( plastic bags, plastic films, geomembranes and containers including bo ...
.
In the evolution of heterogeneous alkene metathesis
Olefin metathesis is an organic reaction that entails the redistribution of fragments of alkenes (olefins) by the scission and regeneration of carbon-carbon double bonds. Because of the relative simplicity of olefin metathesis, it often create ...
catalysts, metallacyclopentanes are invoked as intermediates in the formation of metal alkylidene
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
s from ethylene. Thus, metallacyclopentane intermediates are proposed to isomerize to metallacyclobutane
In organometallic chemistry, a metallacycle is a derivative of a carbocyclic compound wherein a metal has replaced at least one carbon center; this is to some extent similar to heterocycles. Metallacycles appear frequently as reactive intermediate ...
s, which can eliminate alkene giving the alkylidene.
See also
*Metallole Metalloles are derivatives of cyclopentadiene in which the carbon atom at position 5, the saturated carbon, is replaced by a heteroatom. In contrast to its parent compound, the numbering of the metallole starts at the heteroatom. Some of these compo ...
References
External links
*
{{Authority control
Five-membered rings
Heterocyclic compounds