Transition metal ether complex explained

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. 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

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.

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:[1]

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−.

Metal halide complexes

Metal chloride-tetrahydrofuran complexes are especially studied.[6] These compounds are often reagents because they are soluble in organic solvents as well as being anhydrous.

Formula of
metal-chloride-ether complexes 		Coordination
sphere		color
TiO2Cl4yellow[7]
TiO3Cl3blue
[TiCl<sub>3</sub>(thf)<sub>2</sub>]2 TiO2Cl4green[8]
ZrO2Cl4white
HfO2Cl4white
VO3Cl3pink
VCl3(thf)2]2 VO2Cl4red
NbO2Cl4yellow
TaO2Cl4 and TaOCl5[9]
CrO3Cl3pink
MoO2Cl4pink[10]
MoCl4(Et2O)2MoO2Cl4beige[11]
MoO3Cl3red
WCl4(Et2O)2WO2Cl4yellow[12]
MnCl3(thf)3 MnO3Cl3brown-purple[13]
TcO2Cl4yellow
ReO2Cl4green[14]
FeO2Cl3, FeO2Cl4brown[15]
FeO2Cl3[16] the related diethyl ether complex is brown
FeO2Cl3brown
CoO2Cl3, CoO2Cl4blue[17]
[CoCl<sub>2</sub>(dme)]2CoO2Cl3[18]
NiCl2(dimethoxyethane)2NiCl2O4yellow[19]
CuO2Cl4, CuOCl4orange[20]
ZnO2Cl2white[21]

Metal carbonyl complexes

References

  1. 10.1016/j.poly.2016.07.024. 2016 . 117 . Bianchi . Sabrina . Bortoluzzi . Marco . Castelvetro . Valter . Marchetti . Fabio . Pampaloni . Guido . Pinzino . Calogero . Zacchini . Stefano . The reactivity of tungsten hexachloride with tetrahydrofuran and 2-methoxyethanol . Polyhedron . 769–776 . 11568/803763 . free .
  2. 10.1002/(SICI)1521-3773(19981204)37:22<3169::AID-ANIE3169>3.0.CO;2-0. Cationic Homoleptic Vanadium(II), (IV), and (V) Complexes Arising from Protonolysis of [V(NEt2)4] . 1998 . Choukroun . Robert . Moumboko . Pierre . Chevalier . Sandrine . Etienne . Michel . Donnadieu . Bruno . Angewandte Chemie International Edition . 37 . 22 . 3169–3172 . 29711321 .
  3. 10.1021/ja00117a019. 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 . 1995 . Kong . Gapgoung . Harakas . George N. . Whittlesey . Bruce R. . Journal of the American Chemical Society . 117 . 12 . 3502–3509 .
  4. 10.1021/acs.organomet.5b00395. Mono- and Dinuclear Neutral and Cationic Iron(II) Compounds Supported by an Amidinato-diolefin Ligand: Characterization and Catalytic Application . 2015 . Lichtenberg . Crispin . Adelhardt . Mario . Wörle . Michael . Büttner . Torsten . Meyer . Karsten . Grützmacher . Hansjörg . Organometallics . 34 . 12 . 3079–3089 .
  5. 10.1002/zaac.201700367. Reactivity of [Ni(cod)2][Al(ORF)4] towards Small Molecules and Elements . 2018 . Schwab . Miriam M. . Himmel . Daniel . Kacprzak . Sylwia . Radtke . Valentin . Kratzert . Daniel . Yassine . Zeinab . Weis . Philippe . Weber . Stefan . Krossing . Ingo . Zeitschrift für Anorganische und Allgemeine Chemie . 644 . 50–57 .
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  7. 10.1021/ic060896u. Technetium Tetrachloride as a Precursor for Small Technetium(IV) Complexes. 2006. Hagenbach. Adelheid. Yegen. Eda. Abram. Ulrich. Inorganic Chemistry. 45. 18. 7331–7338. 16933935.
  8. 10.1039/dt9930002353. New intermediates for the Synthesis of Olefin Polymerization Catalysts: The Complexes [M<sub>2</sub>(μ-Cl)<sub>2</sub>Cl<sub>4</sub>(THF)<sub>4</sub>] (M = Ti or V, THF = Tetrahydrofuran); Crystal Structures and Properties. 1993. Sobota. Piotr. Ejfler. Jolanta. Szafert. Sławomir. Szczegot. Krzysztof. Sawka-Dobrowolska. Wanda. Journal of the Chemical Society, Dalton Transactions . 15. 2353–2357.
  9. 10.1021/ic00351a005. New Synthetic Routes for the Preparation of Niobium(III) and Tantalum(III) Triangular Cluster Compounds. 1990. Babaian-Kibala. Elizabeth. Cotton. F. Albert. Shang. Maoyu. Inorganic Chemistry. 29. 26. 5148–5156.
  10. Book: 28 . The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes . 1990 . 10.1002/9780470132593.ch7. Dilworth . Jonathan R. . Richards . Raymond L. . Inorganic Syntheses . Inorganic Syntheses . 33–43. 9780470132593 .
  11. Book: 10.1002/9781118744994.ch03. Ether Complexes of Molybdenum(III) and Molybdenum(IV) chlorides . Inorganic Syntheses . 2014 . Maria . Sébastien . Poli . Rinaldo . Inorganic Syntheses: Volume 36 . 15–18 . 9781118744994 .
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  13. 10.1002/zaac.201500106. Solvates of Manganese Trichloride Revisited - Synthesis, Isolation, and Crystal Structure of MnCl3(THF)3. 2015. Nachtigall. Olaf. Pataki. Astrid. Molski. Matthias. Lentz. Dieter. Spandl. Johann. Zeitschrift für Anorganische und Allgemeine Chemie. 641. 6. 1164–1168.
  14. 10.1021/ic060896u. H.-W. . Swidersky . J. . Pebler . K. . Dehnicke . D. . Fenske. Technetium Tetrachloride as a Precursor for Small Technetium(IV) Complexes. Inorganic Chemistry. 1990. 45. 18. 7331–8. 16933935.
  15. 10.1016/S0020-1693(00)85366-9. New polynuclear compounds of iron(II) chloride with oxygen donor ligands Part I. Fe4Cl8(THF)6: Synthesis and a single crystal X-ray structure determination. 1991. Cotton. F. Albert. Luck. Rudy L.. Son. Kyung-Ae. Inorganica Chimica Acta. 179. 11–15.
  16. L. V. Ivakina, N. R. Strel'tsova, V. K. Bel'skii, P. A. Storozhenko, B. M. Bulychev, A. B. Tarasov. Zh.Obshch.Khim. (Russ.J.Gen.Chem.). 1987. 57. 1600.
  17. 10.1016/S0277-5387(00)84976-1. Synthesis, Magnetic Properties and Structure of the [Co<sub>4</sub>(μ<sub>3</sub>-Cl)<sub>2</sub>(μ<sub>2</sub>-Cl)<sub>4</sub>Cl<sub>2</sub>(THF)<sub>6</sub>] Complex. 1993. Sobota. Piotr. Olejnik. Zofia. Utko. Józef. Lis. Tadeusz. Polyhedron. 12. 6. 613–616.
  18. 10.5562/cca1747. Octahedral and Tetrahedral Cobalt(II) Sites in Cobalt Chloride Complexes with Polyethers . 2011 . Petriček . Saša . Croatica Chemica Acta . 515–520 . free .
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