In chemistry, a transition metal ether complex is a

coordination complex A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...

consisting of a

transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that c ...

bonded to one or more

ether In organic chemistry, ethers are a class of compounds that contain an ether group—an oxygen atom connected to two alkyl or aryl groups. They have the general formula , where R and R′ represent the alkyl or aryl groups. Ethers can again b ...

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 ...

. The inventory of complexes is extensive. Common ether ligands are

diethyl ether Diethyl ether, or simply ether, is an organic compound in the ether class with the formula , sometimes abbreviated as (see Pseudoelement symbols). It is a colourless, highly volatile, sweet-smelling ("ethereal odour"), extremely flammable liq ...

and

tetrahydrofuran Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water- miscible organic liquid with low viscosity. It is ...

. Common chelating ether ligands include the glymes,

dimethoxyethane Dimethoxyethane, also known as glyme, monoglyme, dimethyl glycol, ethylene glycol dimethyl ether, dimethyl cellosolve, and DME, is a colorless, aprotic, and liquid ether that is used as a solvent, especially in batteries. Dimethoxyethane is misc ...

(dme) and

diglyme Diglyme, or bis(2-methoxyethyl) ether, is a solvent with a high boiling point. It is an organic compound which is the dimethyl ether of diethylene glycol. (The name ''diglyme'' is a portmanteau of ''diglycol methyl ether''.) It is a colorless liq ...

, and the

crown ether In organic chemistry, crown ethers are cyclic chemical compounds that consist of a ring containing several ether groups (). The most common crown ethers are cyclic oligomers of ethylene oxide, the repeating unit being ethyleneoxy, i.e., . I ...

s. Being lipophilic, metal-ether complexes often exhibit solubility in organic solvents, a property of interest in synthetic chemistry. In contrast, the di-ether 1,4-dioxane is generally a

bridging ligand In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually ...

Bonding, structure, reactions

Ethers are L-type

s. They are σ-donors that exert weak field

s. They resemble water ligands as seen in

aquo complex In chemistry, metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlora ...

es. They do not, however, readily participate in

hydrogen bonding In chemistry, a hydrogen bond (or H-bond) is a primarily electrostatic force of attraction between a hydrogen (H) atom which is covalently bound to a more electronegative "donor" atom or group (Dn), and another electronegative atom bearing ...

. The ether oxygen is nearly trigonal planar in its complexes. Being weakly basic, ether ligands tend to be easily displaceable. Otherwise, ether ligands are relatively unreactive. Cyclic ethers such as thf can ring-open or even deoxygenated when bound to highly electrophilic metal halides. Thus treatment of

tungsten hexachloride Tungsten hexachloride is the chemical compound of tungsten and chlorine with the formula WCl6. This dark violet blue species exists as a volatile solid under standard conditions. It is an important starting reagent in the preparation of tungst ...

with one equivalent of thf gives 1,4-dichlorobutane: : At higher concentrations of thf,

polytetrahydrofuran Polytetrahydrofuran, also called poly(tetramethylene ether) glycol or poly(tetramethylene oxide), is a chemical compound with formula ()''n''OH2 or HO-(-(CH2)4O-)''n''-H. It can be viewed as a polymer of tetrahydrofuran, or as the polyether deriv ...

is produced.

Examples

Homoleptic complexes

Ethers are relatively bulky ligands, thus homoleptic (i.e., all ligands being the same) ether complexes are uncommon. Examples often feature

weakly coordinating anion Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly foun ...

s such as BAr^F₄⁻ and Al(OR^F)₄⁻. * (thf)₆BAr^F₄)₂ * n(thf)₆Mn(CO)₅]₂ * Fe(thf)₆ Ar^F24sub>2 * i(thf)₆Al(OR^F)₄ ]₂

Metal halide complexes

Metal chloride-

complexes are especially studied. These compounds are often reagents because they are soluble in organic solvents as well as being anhydrous.

Metal carbonyl complexes

*M(CO)₅(thf) (M = Cr, Mo, W) *Mo(CO)₃(diglyme)

References

{{Coordination complexes Coordination complexes Ethers