In organometallic chemistry, a "constrained geometry complex" (CGC) is a kind of catalyst used for the production of polyolefins such as

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 ...

and

polypropylene Polypropylene (PP), also known as polypropene, is a thermoplastic polymer used in a wide variety of applications. It is produced via chain-growth polymerization from the monomer propylene. Polypropylene belongs to the group of polyolefins an ...

. The catalyst was one of the first major departures from

metallocene A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are the metallocene d ...

-based catalysts and ushered in much innovation in the development of new plastics.

Structure

CGC complexes feature a pi-bonded moiety (e.g.

cyclopentadienyl Cyclopentadienyl can refer to * Cyclopentadienyl anion, or cyclopentadienide, **Cyclopentadienyl ligand A cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl anion, cyclopentadienyl groups (, abbreviated as Cp−) ...

) linked to one of the other

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 ele ...

s on the same

metal 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 typi ...

centre in such a way that the angle at this metal between the centroid of the pi-system and the additional ligand is smaller than in comparable unbridged complexes. More specifically, the term CGC was used for ansa-bridged cyclopentadienyl amido complexes, although the definition goes far beyond this class of compounds. The term CGC is frequently used in connection with other more or less related ligand systems that may or may not be isolobal and/or

isoelectronic Isoelectronicity is a phenomenon observed when two or more molecules have the same structure (positions and connectivities among atoms) and the same electronic configurations, but differ by what specific elements are at certain locations in th ...

with the ansa-bridged cyclopentadienyl amido ligand system. Furthermore, the term is frequently used for related complexes with long ansa-bridges that induce no strain. Ansa-bridged cyclopentadienyl amido complexes are known for the

Group 3 Group 3 may refer to: *Group 3 element, chemical element classification *Group 3 (racing), FIA classification for auto racing * Group 3, the third tier of races in worldwide Thoroughbred horse racing * Group 3 image format, Group 3 & Group 4 are ...

, 4, 5, 6 and some

Group 8 Group 8 may refer to: * Group 8 element, a series of elements in the Periodic Table * Group 8 Rugby League, a rugby league competition * Group 8 (Sweden), a feminist movement in Sweden * Group VIII, former nomenclature for the noble gas The no ...

metals, with the Group 4 congeners being the most studied ones.

Applications

Like Group 4

s, suitable Group 4 CGCs may be activated for the

polymerisation In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many for ...

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 ...

and

alpha-olefin In organic chemistry, alpha-olefins (or α-olefins) are a family of organic compounds which are alkenes (also known as olefins) with a chemical formula , distinguished by having a double bond at the primary or alpha (α) position.''Petrochemical ...

s by reaction with

co-catalyst Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycl ...

s, e.g.

methylaluminoxane Methylaluminoxane, commonly called MAO, is a mixture of organoaluminium compounds with the approximate formula (Al(CH3)O)''n''. It is usually encountered as a solution in (aromatic) solvents, commonly toluene but also xylene, cumene, or mesitylene ...

(MAO),

tris(pentafluorophenyl)borane Tris(pentafluorophenyl)borane, sometimes referred to as "BCF", is the chemical compound . It is a white, volatile solid. The molecule consists of three pentafluorophenyl groups attached in a "paddle-wheel" manner to a central boron atom; the c ...

s, and

trityl Triphenylmethane, or triphenyl methane, is the hydrocarbon with the formula (C6H5)3CH. This colorless solid is soluble in nonpolar organic solvents and not in water. Triphenylmethane is the basic skeleton of many synthetic dyes called triarylmet ...

borates. The catalytic systems based on CGCs, however, display incorporation of alpha-olefin

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 to a greater extend than comparable metallocene based systems. This superiority of CGCs in copolymerisation reactions is ascribed to (i) a high accessibility of the reactive centre and (ii) a low tendency of the bulk polymer chain to undergo

chain transfer reaction Chain transfer is a polymerization reaction by which the activity of a growing polymer chain is transferred to another molecule. :P• + XR' → PX + R'• Chain transfer reactions reduce the average molecular weight of the final polymer. Chain ...

s. CGC derived polymers are currently marketed by The Dow Chemical Company as part of their INSITE technology. Beyond the use of CGCs for polymerisation reactions, a number of other transformations catalysed by CGCs (both of Group 3 and 4 metals) have been reported from academic laboratories. These include the application of CGCs as catalysts for

hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate org ...

imine In organic chemistry, an imine ( or ) is a functional group or organic compound containing a carbon–nitrogen double bond (). The nitrogen atom can be attached to a hydrogen or an organic group (R). The carbon atom has two additional single bo ...

hydroboration In organic chemistry, hydroboration refers to the addition of a hydrogen- boron bond to certain double and triple bonds involving carbon (, , , and ). This chemical reaction is useful in the organic synthesis of organic compounds. Hydroboration ...

of alkenes, carboalumination of alkenes,

hydrosilylation Hydrosilylation, also called catalytic hydrosilation, describes the addition of Si-H bonds across unsaturated bonds."Hydrosilylation A Comprehensive Review on Recent Advances" B. Marciniec (ed.), Advances in Silicon Science, Springer Science, 2009 ...

of alkenes, hydroamination/cyclisation of alpha ,omega-aminoalkenes and dimerisation of terminal

alkyne \ce \ce Acetylene \ce \ce \ce Propyne \ce \ce \ce \ce 1-Butyne In organic chemistry, an alkyne is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond. The simplest acyclic alkynes with only one triple bond and no ...

History

The first CGC was reported by Shapiro and Bercaw for a

scandium Scandium is a chemical element with the symbol Sc and atomic number 21. It is a silvery-white metallic d-block element. Historically, it has been classified as a rare-earth element, together with yttrium and the Lanthanides. It was discovere ...

complex. The following year patents were issued to

The Dow Chemical Company The Dow Chemical Company, officially Dow Inc., is an American multinational chemical corporation headquartered in Midland, Michigan, United States. The company is among the three largest chemical producers in the world. Dow manufactures plastics ...

and

Exxon ExxonMobil Corporation (commonly shortened to Exxon) is an American multinational oil and gas corporation headquartered in Irving, Texas. It is the largest direct descendant of John D. Rockefeller's Standard Oil, and was formed on November ...

for applications in alkene polymerization. and today are made at the billion pound scale.Dow Chemical. Solutionism at Work: 2011 Databook, www.dow.com/financial, Form No. 161-00770, April 2012, page 62.

References

{{Reflist Organometallic chemistry Metal amides