Transition metal ether complex

Last updated
Structure of the ether complex HfCl4(thf)2. VEHZAJ.svg
Structure of the ether complex HfCl4(thf)2.

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.

Contents

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. CoCl2(dioxane)XUBHEI).jpg
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.

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−.

Metal halide complexes

Structure of NiI2(dme)2 as determined by X-ray crystallography. The sum of the angles at O is 352deg, indicating a nearly planar ether oxygen. Color code: O = red, I = purple, Ni = blue, C = black. NiI2(dme)2.png
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.
Structure of FeCl3(diethylether)2. Color code: Cl=green,Fe = blue, O = red. UJIMUV.jpg
Structure of FeCl3(diethylether)2. 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
metal-chloride-ether complexes		Coordination
sphere		color
TiCl4(thf)2 TiO2Cl4yellow [13]
TiCl3(thf)3 TiO3Cl3blue [12]
[TiCl3(thf)2]2TiO2Cl4green [14]
ZrCl4(thf)2 ZrO2Cl4white [12]
HfCl4(thf)2 HfO2Cl4white [12]
VCl3(thf)3 VO3Cl3pink [12]
VCl3(thf)2]2VO2Cl4red [14]
NbCl4(thf)2 NbO2Cl4yellow [15]
Ta3Cl9(thf)4 TaO2Cl4 and TaOCl5 [15]
CrCl3(thf)3 CrO3Cl3pink [12] [16]
MoCl4(thf)2 MoO2Cl4pink [17]
MoCl4(Et2O)2MoO2Cl4beige [18]
MoCl3(thf)3 MoO3Cl3red [17]
WCl4(Et2O)2 WO2Cl4yellow [19]
MnCl3(thf)3MnO3Cl3brown-purple [20]
TcCl4(thf)2 TcO2Cl4yellow [13]
ReCl4(thf)2 ReO2Cl4green [21]
Fe4Cl8(thf)6 FeO2Cl3, FeO2Cl4brown [22]
FeCl3(thf)2 FeO2Cl3 [23] the related diethyl ether complex is brown
FeCl3(OEt2)2 FeO2Cl3brown [11]
Co4Cl8(thf)6 CoO2Cl3, CoO2Cl4blue [24]
[CoCl2(dme)]2CoO2Cl3 [25]
NiCl2(dimethoxyethane)2 NiCl2O4yellow [26]
[Cu2Cl4(thf)3]n CuO2Cl4, CuOCl4orange [27]
ZnCl2(thf)2 ZnO2Cl2white [16]

Metal carbonyl complexes

Related Research Articles

<span class="mw-page-title-main">Chromium hexacarbonyl</span> Chemical compound

Chromium hexacarbonyl is a chromium(0) organometallic compound with the formula Cr(CO)6. It is a homoleptic complex, which means that all the ligands are identical. It is a colorless crystalline air-stable solid, with a high vapor pressure.

<span class="mw-page-title-main">Scandium chloride</span> Chemical compound

Scandium(III) chloride is the inorganic compound with the formula ScCl3. It is a white, high-melting ionic compound, which is deliquescent and highly water-soluble. This salt is mainly of interest in the research laboratory. Both the anhydrous form and hexahydrate (ScCl3•6H2O) are commercially available.

Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important catalyst for the manufacture of polyolefins.

<span class="mw-page-title-main">Vanadium(III) chloride</span> Chemical compound

Vanadium(III) chloride describes the inorganic compound with the formula VCl3 and its hydrates. It forms a purple anhydrous form and a green hexahydrate [VCl2(H2O)4]Cl·2H2O. These hygroscopic salts are common precursors to other vanadium(III) complexes and is used as a mild reducing agent.

<span class="mw-page-title-main">Molybdenum(V) chloride</span> Chemical compound

Molybdenum(V) chloride is the inorganic compound with the empirical formula MoCl5. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents.

<span class="mw-page-title-main">Titanium(II) chloride</span> Chemical compound

Titanium(II) chloride is the chemical compound with the formula TiCl2. The black solid has been studied only moderately, probably because of its high reactivity. Ti(II) is a strong reducing agent: it has a high affinity for oxygen and reacts irreversibly with water to produce H2. The usual preparation is the thermal disproportionation of TiCl3 at 500 °C. The reaction is driven by the loss of volatile TiCl4:

<span class="mw-page-title-main">Tungsten dichloride dioxide</span> Chemical compound

Tungsten dichloride dioxide, or Tungstyl chloride is the chemical compound with the formula WO2Cl2. It is a yellow-colored solid. It is used as a precursor to other tungsten compounds. Like other tungsten halides, WO2Cl2 is sensitive to moisture, undergoing hydrolysis.

<span class="mw-page-title-main">Metal bis(trimethylsilyl)amides</span>

Metal bis(trimethylsilyl)amides are coordination complexes composed of a cationic metal M with anionic bis(trimethylsilyl)amide ligands (the −N 2 monovalent anion, or −N 2 monovalent group, and are part of a broader category of metal amides.

<span class="mw-page-title-main">Bis(dinitrogen)bis(1,2-bis(diphenylphosphino)ethane)molybdenum(0)</span> Chemical compound

trans-Bis(dinitrogen)bis[1,2-bis(diphenylphosphino)ethane]molybdenum(0) is a coordination complex with the formula Mo(N2)2(dppe)2. It is a relatively air stable yellow-orange solid. It is notable as being the first discovered dinitrogen containing complex of molybdenum.

<span class="mw-page-title-main">Transition metal pyridine complexes</span>

Transition metal pyridine complexes encompass many coordination complexes that contain pyridine as a ligand. Most examples are mixed-ligand complexes. Many variants of pyridine are also known to coordinate to metal ions, such as the methylpyridines, quinolines, and more complex rings.

Nitride fluorides containing nitride and fluoride ions with the formula NF4-. They can be electronically equivalent to a pair of oxide ions O24-. Nitride fluorides were discovered in 1996 by Lavalle et al. They heated diammonium technetium hexafluoride to 300 °C to yield TcNF. Another preparation is to heat a fluoride compound with a nitride compound in a solid state reaction. The fluorimido ion is F-N2- and is found in a rhenium compound.

<span class="mw-page-title-main">Transition metal chloride complex</span> Coordination complex

In chemistry, a transition metal chloride complex is a coordination complex that consists of a transition metal coordinated to one or more chloride ligand. The class of complexes is extensive.

Sulfidostannates, or thiostannates are chemical compounds containing anions composed of tin linked with sulfur. They can be considered as stannates with sulfur substituting for oxygen. Related compounds include the thiosilicates, and thiogermanates, and by varying the chalcogen: selenostannates, and tellurostannates. Oxothiostannates have oxygen in addition to sulfur. Thiostannates can be classed as chalcogenidometalates, thiometallates, chalcogenidotetrelates, thiotetrelates, and chalcogenidostannates. Tin is almost always in the +4 oxidation state in thiostannates, although a couple of mixed sulfides in the +2 state are known,

A chloride nitride is a mixed anion compound containing both chloride (Cl−) and nitride ions (N3−). Another name is metallochloronitrides. They are a subclass of halide nitrides or pnictide halides.

Phosphanides are chemicals containing the [PH2]− anion. This is also known as the phosphino anion or phosphido ligand. The IUPAC name can also be dihydridophosphate(1−).

Sulfidogermanates or thiogermanates are chemical compounds containing anions with sulfur atoms bound to germanium. They are in the class of chalcogenidotetrelates. Related compounds include thiosilicates, thiostannates, selenidogermanates, telluridogermanates and selenidostannates.

An iodide nitride is a mixed anion compound containing both iodide (I−) and nitride ions (N3−). Another name is metalloiodonitrides. They are a subclass of halide nitrides or pnictide halides. Some different kinds include ionic alkali or alkaline earth salts, small clusters where metal atoms surround a nitrogen atom, layered group 4 element 2-dimensional structures, and transition metal nitrido complexes counter-balanced with iodide ions. There is also a family with rare earth elements and nitrogen and sulfur in a cluster.

Carbide chlorides are mixed anion compounds containing chloride anions and anions consisting entirely of carbon. In these compounds there is no bond between chlorine and carbon. But there is a bond between a metal and carbon. Many of these compounds are cluster compounds, in which metal atoms encase a carbon core, with chlorine atoms surrounding the cluster. The chlorine may be shared between clusters to form polymers or layers. Most carbide chloride compounds contain rare earth elements. Some are known from group 4 elements. The hexatungsten carbon cluster can be oxidised and reduced, and so have different numbers of chlorine atoms included.

Selenidostannates are chemical compounds which contain anionic units of selenium connected to tin. They can be considered as stannates where selenium substitutes for oxygen. Similar compounds include the selenogermanates and thiostannates. They are in the category of chalcogenidotetrelates or more broadly chalcogenometallates.

Manganese(III) chloride is the hypothetical inorganic compound with the formula MnCl3.

References

  1. ↑ Duraj, S. A.; Towns; Baker; Schupp, J. (1990). "Structure of cis-Tetrachlorobis(tetrahydrofuran)hafnium(IV)". Acta Crystallographica . C46 (5): 890–2. doi:10.1107/S010827018901382X.
  2. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. 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. doi:10.1021/ja902101x. PMID   19402661.
  4. 1 2 Schubert, U.; Friedrich, P.; Orama, O. (1978). "Kristall- und molekülstruktur von pentacarbonyltetrahydrofuran-chrom(0)". Journal of Organometallic Chemistry. 144 (2): 175–179. doi:10.1016/S0022-328X(00)84160-1.
  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 .
  6. ↑ Choukroun, Robert; Moumboko, Pierre; Chevalier, Sandrine; Etienne, Michel; Donnadieu, Bruno (1998). "Cationic Homoleptic Vanadium(II), (IV), and (V) Complexes Arising from Protonolysis of [V(NEt2)4]". Angewandte Chemie International Edition. 37 (22): 3169–3172. doi:10.1002/(SICI)1521-3773(19981204)37:22<3169::AID-ANIE3169>3.0.CO;2-0. PMID   29711321.
  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. 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.
  9. ↑ Schwab, Miriam M.; Himmel, Daniel; Kacprzak, Sylwia; Radtke, Valentin; Kratzert, Daniel; Yassine, Zeinab; Weis, Philippe; Weber, Stefan; Krossing, Ingo (2018). "Reactivity of [Ni(cod)2][Al(ORF)4] towards Small Molecules and Elements". Zeitschrift für Anorganische und Allgemeine Chemie. 644: 50–57. doi:10.1002/zaac.201700367.
  10. ↑ Crochet, Aurélien; Fromm, Katharina M. (2010). "Polyether Adducts of d-Block Metal Compounds as Starting Materials for New Cluster Compounds" (PDF). Zeitschrift für anorganische und allgemeine Chemie. 636 (8): 1484–1496. doi:10.1002/zaac.201000022.
  11. 1 2 Spandl, Johann; Kusserow, M.; Brüdgam, I. (2003). "Alkoxo-Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(Ot Bu)6], [Fe2Cl2(Ot Bu)4], [Fe2Cl4(Ot Bu)2] und [N(n Bu)4]2[Fe6OCl6(OMe)12]". Zeitschrift für anorganische und allgemeine Chemie. 629 (6): 968–974. doi: 10.1002/zaac.200300008 .
  12. 1 2 3 4 5 6 Manzer, L. E. (1982). Tetrahydrofuran Complexes of Selected Early Transition Metals. Inorganic Syntheses. Vol. 21. pp. 135–140. doi:10.1002/9780470132524.ch31.
  13. 1 2 Hagenbach, Adelheid; Yegen, Eda; Abram, Ulrich (2006). "Technetium Tetrachloride as a Precursor for Small Technetium(IV) Complexes". Inorganic Chemistry. 45 (18): 7331–7338. doi:10.1021/ic060896u. PMID   16933935.
  14. 1 2 Sobota, Piotr; Ejfler, Jolanta; Szafert, Sławomir; Szczegot, Krzysztof; Sawka-Dobrowolska, Wanda (1993). "New intermediates for the Synthesis of Olefin Polymerization Catalysts: The Complexes [M2(μ-Cl)2Cl4(THF)4] (M = Ti or V, THF = Tetrahydrofuran); Crystal Structures and Properties". Journal of the Chemical Society, Dalton Transactions (15): 2353–2357. doi:10.1039/dt9930002353.
  15. 1 2 Babaian-Kibala, Elizabeth; Cotton, F. Albert; Shang, Maoyu (1990). "New Synthetic Routes for the Preparation of Niobium(III) and Tantalum(III) Triangular Cluster Compounds". Inorganic Chemistry. 29 (26): 5148–5156. doi:10.1021/ic00351a005.
  16. 1 2 Boudjouk, Philip; So, Jeung-Ho (1992). "Solvated and Unsolvated Anhydrous Metal Chlorides from Metal Chloride Hydrates". Inorganic Syntheses. Inorganic Syntheses. Vol. 29. pp. 108–111. doi:10.1002/9780470132609.ch26. ISBN   9780470132609.
  17. 1 2 Dilworth, Jonathan R.; Richards, Raymond L. (1990). "The Synthesis of Molybdenum and Tungsten Dinitrogen Complexes". Inorganic Syntheses. Inorganic Syntheses. Vol. 28. pp. 33–43. doi:10.1002/9780470132593.ch7. ISBN   9780470132593.
  18. ↑ Maria, Sébastien; Poli, Rinaldo (2014). "Ether Complexes of Molybdenum(III) and Molybdenum(IV) chlorides". Inorganic Syntheses: Volume 36 (PDF). Inorganic Syntheses. pp. 15–18. doi:10.1002/9781118744994.ch03. ISBN   9781118744994.
  19. ↑ Schäfer, André (2021). "The Decades-Old Mystery of Bis(diethyl ether)tungsten(IV) Chloride Solved". Acta Crystallographica Section C Structural Chemistry. 77 (4): 167–168. doi:10.1107/S2053229621002461. PMC   8020884 . PMID   33818437.
  20. ↑ Nachtigall, Olaf; Pataki, Astrid; Molski, Matthias; Lentz, Dieter; Spandl, Johann (2015). "Solvates of Manganese Trichloride Revisited - Synthesis, Isolation, and Crystal Structure of MnCl3(THF)3". Zeitschrift für Anorganische und Allgemeine Chemie. 641 (6): 1164–1168. doi:10.1002/zaac.201500106.
  21. ↑ Swidersky, H.-W.; Pebler, J.; Dehnicke, K.; Fenske, D. (1990). "Technetium Tetrachloride as a Precursor for Small Technetium(IV) Complexes". Inorganic Chemistry. 45 (18): 7331–8. doi:10.1021/ic060896u. PMID   16933935.
  22. ↑ Cotton, F. Albert; Luck, Rudy L.; Son, Kyung-Ae (1991). "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". Inorganica Chimica Acta. 179: 11–15. doi:10.1016/S0020-1693(00)85366-9.
  23. ↑ L. V. Ivakina, N. R. Strel'tsova, V. K. Bel'skii, P. A. Storozhenko, B. M. Bulychev, A. B. Tarasov (1987). Zh.Obshch.Khim. (Russ.J.Gen.Chem.). 57: 1600.{{cite journal}}: Missing or empty |title= (help)CS1 maint: multiple names: authors list (link)
  24. ↑ Sobota, Piotr; Olejnik, Zofia; Utko, Józef; Lis, Tadeusz (1993). "Synthesis, Magnetic Properties and Structure of the [Co4(μ3-Cl)2(μ2-Cl)4Cl2(THF)6] Complex". Polyhedron. 12 (6): 613–616. doi:10.1016/S0277-5387(00)84976-1.
  25. ↑ Petriček, Saša (2011). "Octahedral and Tetrahedral Cobalt(II) Sites in Cobalt Chloride Complexes with Polyethers". Croatica Chemica Acta: 515–520. doi: 10.5562/cca1747 .
  26. ↑ Ward, Laird G. L. (1972). "Anhydrous Nickel(II) Halides and their Tetrakis(ethanol) and 1,2-Dimethoxyethane Complexes". Inorganic Syntheses. Inorganic Syntheses. Vol. 13. pp. 154–164. doi:10.1002/9780470132449.ch30. ISBN   9780470132449.
  27. ↑ Becker, Sabine; Dürr, Maximilian; Miska, Andreas; Becker, Jonathan; Gawlig, Christopher; Behrens, Ulrich; Ivanović-Burmazović, Ivana; Schindler, Siegfried (2016). "Copper Chloride Catalysis: Do μ4-Oxido Copper Clusters Play a Significant Role?". Inorganic Chemistry. 55 (8): 3759–3766. doi:10.1021/acs.inorgchem.5b02576. PMID   27045752.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.