# Transition metal ether complex

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In [chemistry](/source/Chemistry), a **transition metal ether complex** is a [coordination complex](/source/Coordination_complex) consisting of a [transition metal](/source/Transition_metal) bonded to one or more [ether](/source/Ether) [ligand](/source/Ligand). The inventory of complexes is extensive.[1] Common ether ligands are [diethyl ether](/source/Diethyl_ether) and [tetrahydrofuran](/source/Tetrahydrofuran). Common chelating ether ligands include the [glymes](/source/Glycol_ethers), [dimethoxyethane](/source/Dimethoxyethane) (dme) and [diglyme](/source/Diglyme), and the [crown ethers](/source/Crown_ether). 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](/source/Bridging_ligand).

## Bonding, structure, reactions

Ethers are L-type [ligands](/source/Ligand). They are σ-donors that exert [weak field](/source/Crystal_field_theory) [ligands](/source/Ligand). They resemble water ligands as seen in [aquo complexes](/source/Aquo_complex). They do not, however, readily participate in [hydrogen bonding](/source/Hydrogen_bonding). The ether oxygen is nearly trigonal planar in its complexes.[2]

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](/source/Tungsten_hexachloride) with one equivalent of thf gives [1,4-dichlorobutane](/source/1,4-Dichlorobutane):[3]

- WCl6 + OC4H8 → WOCl4 + ClCH2CH2CH2CH2Cl

At higher concentrations of thf, [polytetrahydrofuran](/source/Polytetrahydrofuran) 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 anions](/source/Weakly_coordinating_anion) such as BArF4− and Al(ORF)4−.

- [V(thf)6](BArF4)2[4]
- [Mn(thf)6](Mn(CO)5]2[5]
- [[Fe(thf)6]][BArF24]2[6]
- [Ni(thf)6][Al(ORF)4 ]2[7]

### Metal halide complexes

Metal chloride-[tetrahydrofuran](/source/Tetrahydrofuran) complexes are especially studied.[8] These compounds are often reagents because they are soluble in organic solvents as well as being anhydrous.

Formula of M-Cl-ether complexes Coordination sphere color and comment ScCl3(thf)3 mer-ScO3Cl3 colorless[9] TiCl4(Et2O)2 cis-TiO2Cl4 yellow[10] TiCl4(thf)2 cis and trans-TiO2Cl4 yellow[11][12] Both cis and trans isomers have been reported TiCl3(thf)3 mer-TiO3Cl3[13] blue[8] [TiCl3(thf)2]2 TiO2Cl4 green[14] ZrCl4(Et2O)2 trans-ZrO2Cl4[15] white ZrCl4(thf)2 cis-ZrO2Cl4 white[8] HfCl4(thf)2 cis-HfO2Cl4 white[8] VCl3(thf)3 mer-VO3Cl3[16] pink[8] [VCl3(thf)2]2 trans-VO2Cl4 red[14] NbCl4(Et2O)2 trans-NbO2Cl4 yellow[17] NbCl4(thf)2 trans-NbO2Cl4 yellow[18] Ta3Cl9(thf)4 TaO2Cl4 and TaOCl5[18] green CrCl3(thf)3 mer-CrO3Cl3[16] pink[8][19] MoCl4(thf)2 trans-MoO2Cl4 pink[20] MoCl4(Et2O)2 trans-MoO2Cl4 beige[21] MoCl3(thf)3 mer-MoO3Cl3[22] red[20][23] WCl3(thf)3 mer-WO3Cl3[24] yellow WCl4(Et2O)2 trans-WO2Cl4 yellow[25][26] MnCl3(thf)3 mer-MnO3Cl3 brown-purple[27] TcCl4(thf)2 cis-TcO2Cl4 yellow[28] ReCl4(thf)2 cis-ReO2Cl4 green[29] Fe4Cl8(thf)6 FeO2Cl3, FeO2Cl4 brown[30] FeCl3(thf)2 FeO2Cl3[31] the related diethyl ether complex is brown FeCl3(OEt2)2 FeO2Cl3 brown[32] Co4Cl8(thf)6 CoO2Cl3, CoO2Cl4 blue[33] isostructural with Fe analogue [CoCl2(dme)]2 CoO2Cl3 pink[34] NiCl2(dimethoxyethane)2 cis-NiCl2O4 yellow[35] [Cu2Cl4(thf)3]n CuO2Cl4, CuOCl4 orange[36] ZnCl2(thf)2 ZnO2Cl2 white[19]

### Metal carbonyl complexes

- M(CO)5(thf) (M = Cr, Mo, W)[2]
- Mo(CO)3(diglyme)

## References

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