Vanadium oxytrichloride
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| Names | |
|---|---|
| IUPAC name
Vanadium trichloride oxide | |
Other names
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| Identifiers | |
| 3D model (JSmol) |
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| ChemSpider | |
| ECHA InfoCard | 100.028.892 |
| EC Number | 231-780-2 |
| MeSH | trichlorooxo+vanadium |
| RTECS number | YW2975000 |
| UN number | 2443 |
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| Properties | |
| VOCl 3 | |
| Molar mass | 173.300 g mol−1 |
| Appearance | yellow liquid |
| Density | 1.826 g mL−1 |
| Melting point | −76.5 °C (−105.7 °F; 196.7 K) |
| Boiling point | 126.7 °C (260.1 °F; 399.8 K) |
| Decomposes | |
| Vapor pressure | 1.84 kPa (at 20 °C) |
| Structure | |
| Tetrahedral | |
| Hazards | |
| GHS pictograms |   |
| GHS signal word | DANGER |
| H301, H314 | |
| P280, P301+310, P305+351+338, P310 | |
| NFPA 704 | |
| Lethal dose or concentration (LD, LC): | |
| LD50 (median dose) |
140 mg kg−1 (oral, rat) |
| Related compounds | |
| Related vanadiums |
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| Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
 verify (what is  ?) | |
| Infobox references | |
Vanadium oxytrichloride is the inorganic compound with the formula VOCl3. This yellow distillable liquid hydrolyzes readily in air. It is an oxidant. It is used as a reagent in organic synthesis.[1] Samples often appear red or orange owing to an impurity of vanadium tetrachloride.[2]
Properties
VOCl3 is a vanadium compound with vanadium in the +5 oxidation state and as such is diamagnetic. It is tetrahedral with O-V-Cl bond angles of 111° and Cl-V-Cl bond angles of 108°. The V-O and V-Cl bond lengths are 157 and 214 pm, respectively. VOCl3 is highly reactive toward water and evolves HCl upon standing. It is soluble in nonpolar solvents such as benzene, CH2Cl2, and hexane. In some aspects, the chemical properties of VOCl3 and POCl3 are similar. One distinction is that VOCl3 is a strong oxidizing agent, whereas the phosphorus compound is not.[3]
Preparation
VOCl3 arises by the chlorination of V2O5. The reaction proceeds near 600 °C:[4]
- 3 Cl2 + V2O5 → 2 VOCl3 + 1.5 O2
When the V2O5 is used as an intimate mixture with carbon, the synthesis proceeds at 200–400 °C; in this case the carbon serves as a deoxygenation agent akin to its use in the Kroll process for the manufacturing of TiCl4 from TiO2.
Vanadium(III) oxide can also be used as a precursor:[2]
- 3 Cl2 + V2O3 → 2 VOCl3 + 0.5 O2
A more typical laboratory synthesis involves the chlorination of V2O5 using SOCl2.[5]
- V2O5 + 3 SOCl2 → 2 VOCl3 + 3 SO2
Reactions
Hydrolysis and alcoholysis
Vanadium oxytrichloride quickly hydrolyzes resulting in vanadium pentoxide and hydrochloric acid. In the picture, orange V2O5 can be seen forming on the walls of the beaker. An intermediate in this process is VO2Cl:
- 2 VOCl3 + 3 H2O → V2O5 + 6 HCl
VOCl3 reacts with alcohols especially in the presence of a proton-acceptor (e.g. Et3N) to give alkoxides:
- VOCl3 + 3 ROH → VO(OR)3 + 3 HCl (R = Me, Ph, etc.)
Interconversions to other V-O-Cl compounds
VOCl3 is also used in the synthesis of VOCl2.
- V2O5 + 3 VCl3 + VOCl3 → 6 VOCl2
Dioxovanadium monochloride can be prepared by an unusual reaction involving Cl2O.[6]
- VOCl3 + Cl2O → VO2Cl + 2 Cl2
At >180 °C, VO2Cl decomposes to V2O5 and VOCl3. Similarly, VOCl2 also decomposes to give VOCl3, together with VOCl.
Adduct formation
VOCl3 is strongly Lewis acidic, as demonstrated by its tendency to form adducts with various bases such as MeCN and amines. In forming the adducts, vanadium changes from four-coordinate tetrahedral geometry to six-coordinate octahedral geometry:
- VOCl3 + 2 H2NEt → VOCl3(H2NEt)2
VOCl3 in alkene polymerization
VOCl3 is used as a catalyst or precatalytst in production of ethylene-propylene rubbers (EPDM).
References
- ↑ M. O'Brien, B. Vanasse (2001). Encyclopedia of Reagents for Organic Synthesis.
- 1 2 F. E. Brown, F. A. Griffitts (1939). "Hypovanadous Oxide and Vanadium Oxytrichloride". Inorg. Syn. I: 106–108. doi:10.1002/9780470132326.ch38.
- ↑ A. Earnshaw, N. Greenwood (1997). The Chemistry of the Elements - Second Edition. pp. 513–514.
- ↑ A. Holleman, E. Wiberg (from). Inorganic Chemistry. Check date values in:
|date=(help) - ↑ G. Brauer "Vanadium oxytrichloride" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1264.
- ↑ Oppermann, H. (1967). "Untersuchungen an Vanadinoxidchloriden und Vanadinchloriden. I. Gleichgewichte mit VOCl3, VO2Cl und VOCl2". Zeitschrift für anorganische und allgemeine Chemie. 351 (3-4): 113–126. doi:10.1002/zaac.19673510302.