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Transition metal ether complex

Structure of the ether complex HfCl4(thf)2fwn[1]

In chemistry, a transition metal ether complex is a coordination complex consisting of a transition metal bonded to one or more ether ligand. The inventory of complexes is extensive.[2] Common ether ligands are diethyl ether and tetrahydrofuran. Common chelating ether ligands include the glymes, dimethoxyethane (dme) and diglyme, and the crown ethers. 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.

Bonding, structure, reactions

In almost all of its complexes, dioxane is a bridging, not chelating, ligand. Structure of the coordination polymer of cobalt(II) chloride and 1,4-dioxane.[3]

Ethers are L-type ligands. They are σ-donors that exert weak field ligands. They resemble water ligands as seen in aquo complexes. They do not, however, readily participate in hydrogen bonding. The ether oxygen is nearly trigonal planar in its complexes.[4]

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 with one equivalent of thf gives 1,4-dichlorobutane:[5]

WCl6 + OC4H8 → WOCl4 + ClCH2CH2CH2CH2Cl

At higher concentrations of thf, 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 such as BArF4− and Al(ORF)4−.

  • [V(thf)6](BArF4)2[6]
  • [Mn(thf)6](Mn(CO)5]2[7]
  • [[Fe(thf)6]][BArF24]2[8]
  • [Ni(thf)6][Al(ORF)4 ]2[9]

Metal halide complexes

Structure of NiI2(dme)2 as determined by X-ray crystallography. The sum of the angles at O is 352°, indicating a nearly planar ether oxygen. Color code: O = red, I = purple, Ni = blue, C = black.[10]
Structure of FeCl3(diethylether)2.[11] Color code: Cl=green, Fe = blue, O = red.

Metal chloride-tetrahydrofuran complexes are especially studied.[12] 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[13]
TiCl4(Et2O)2 cis-TiO2Cl4 yellow[14]
TiCl4(thf)2 cis and trans-TiO2Cl4 yellow[15][16] Both cis and trans isomers have been reported
TiCl3(thf)3 mer-TiO3Cl3[17] blue[12]
[TiCl3(thf)2]2 TiO2Cl4 green[18]
ZrCl4(Et2O)2 trans-ZrO2Cl4[19] white
ZrCl4(thf)2 cis-ZrO2Cl4 white[12]
HfCl4(thf)2 cis-HfO2Cl4 white[12]
VCl3(thf)3 mer-VO3Cl3[20] pink[12]
[VCl3(thf)2]2 trans-VO2Cl4 red[18]
NbCl4(Et2O)2 trans-NbO2Cl4 yellow[21]
NbCl4(thf)2 trans-NbO2Cl4 yellow[22]
Ta3Cl9(thf)4 TaO2Cl4 and TaOCl5[22] green
CrCl3(thf)3 mer-CrO3Cl3[20] pink[12][23]
MoCl4(thf)2 trans-MoO2Cl4 pink[24]
MoCl4(Et2O)2 trans-MoO2Cl4 beige[25]
MoCl3(thf)3 mer-MoO3Cl3[26] red[24][27]
WCl3(thf)3 mer-WO3Cl3[28] yellow
WCl4(Et2O)2 trans-WO2Cl4 yellow[29][30]
MnCl3(thf)3 mer-MnO3Cl3 brown-purple[31]
TcCl4(thf)2 cis-TcO2Cl4 yellow[32]
ReCl4(thf)2 cis-ReO2Cl4 green[33]
Fe4Cl8(thf)6 FeO2Cl3, FeO2Cl4 brown[34]
FeCl3(thf)2 FeO2Cl3[35] the related diethyl ether complex is brown
FeCl3(OEt2)2 FeO2Cl3 brown[11]
Co4Cl8(thf)6 CoO2Cl3, CoO2Cl4 blue[36] isostructural with Fe analogue
[CoCl2(dme)]2 CoO2Cl3 pink[37]
NiCl2(dimethoxyethane)2 cis-NiCl2O4 yellow[38]
[Cu2Cl4(thf)3]n CuO2Cl4, CuOCl4 orange[39]
ZnCl2(thf)2 ZnO2Cl2 white[23]

Metal carbonyl complexes

  • M(CO)5(thf) (M = Cr, Mo, W)[4]
  • Mo(CO)3(diglyme)

References

  1. ^ Duraj, S. A.; Towns; Baker; Schupp, J. (1990). "Structure of cis-Tetrachlorobis(tetrahydrofuran)hafnium(IV)". Acta Crystallographica. C46 (5): 890–2. Bibcode:1990AcCrC..46..890D. doi:10.1107/S010827018901382X.
  2. ^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. doi:10.1016/C2009-0-30414-6. ISBN 978-0-08-037941-8.
  3. ^ Duan, Zhiming; Zhang, Yan; Zhang, Bin; Zhu, Daoben (2009). "Crystal-to-Crystal Transformation from Antiferromagnetic Chains into a Ferromagnetic Diamondoid Framework". Journal of the American Chemical Society. 131 (20): 6934–6935. Bibcode:2009JAChS.131.6934D. doi:10.1021/ja902101x. PMID 19402661.
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  5. ^ Bianchi, Sabrina; Bortoluzzi, Marco; Castelvetro, Valter; Marchetti, Fabio; Pampaloni, Guido; Pinzino, Calogero; Zacchini, Stefano (2016). "The reactivity of tungsten hexachloride with tetrahydrofuran and 2-methoxyethanol". Polyhedron. 117: 769–776. doi:10.1016/j.poly.2016.07.024. hdl:11568/803763.
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  7. ^ Kong, Gapgoung; Harakas, George N.; Whittlesey, Bruce R. (1995). "An Unusual Transition Metal Cluster Containing a Seven Metal Atom Plane. Syntheses and Crystal Structures of [Mn][Mn7(THF)6(CO)12]2, Mn3(THF)2(CO)10, and [Mn(THF)6][Mn(CO)5]2". Journal of the American Chemical Society. 117 (12): 3502–3509. Bibcode:1995JAChS.117.3502K. doi:10.1021/ja00117a019.
  8. ^ Lichtenberg, Crispin; Adelhardt, Mario; Wörle, Michael; Büttner, Torsten; Meyer, Karsten; Grützmacher, Hansjörg (2015). "Mono- and Dinuclear Neutral and Cationic Iron(II) Compounds Supported by an Amidinato-diolefin Ligand: Characterization and Catalytic Application". Organometallics. 34 (12): 3079–3089. doi:10.1021/acs.organomet.5b00395.
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Prefix: a b c d e f g h i j k l m n o p q r s t u v w x y z 0 1 2 3 4 5 6 7 8 9

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