Bromopentacarbonylrhenium(I)
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| Names | |
|---|---|
| IUPAC name
Bromidopentacarbonylrhenium | |
| Identifiers | |
14220-21-4  | |
| ECHA InfoCard | 100.034.607 |
| Properties | |
| Re(CO)5Br | |
| Molar mass | 406.16 g/mol |
| Appearance | colorless |
| Melting point | sublimes 85-90 °C (0.2 mm Hg) |
| Solubility in chlorocarbons | soluble |
| Hazards | |
| EU classification (DSD) |
Toxic (T) |
| R-phrases | R23/24/25 R36/37/38 |
| S-phrases | S26 S28 S36/37/39 S45 |
| Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |
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| Infobox references | |
Bromopentacarbonylrhenium(I) is an inorganic compound of rhenium, commonly used for the syntheses of other rhenium complexes.
Preparation
Bromopentacarbonylrhenium(I) is commercially available. It is also easily and inexpensively synthesized by the oxidation of dirhenium decacarbonyl with bromine:[1]
- Re2(CO)10 + Br2 → 2 ReBr(CO)5
It was first prepared by the "reductive carbonylation" of rhenium(III) bromide:[2]
- ReBr3 + 2 Cu + 5 CO → BrRe(CO)5 + 2 CuBr
Copper(I) bromide is a byproduct.
Reactions
Bromopentacarbonylrhenium(I) is a useful intermediate to other rhenium complexes. For example, it reacts with zinc and acetic acid to give pentacarbonylhydridorhenium (ReH(CO)5).[3]
- Re(CO)5Br + Zn + HO2CCH3 → ReH(CO)5 + ZnBrO2CCH3
It also reacts with tetraethylammonium bromide in diglyme to give [NEt4]2[ReBr3(CO)3)], an important precursor to compounds containing the rhenium tricarbonyl fragment.[4]
Refluxing bromopentacarbonylrhenium(I) in water also provides access to the rhenium tricarbonyl fragment:
- ReBr(CO)5 + 3 H2O → [Re(H2O)3(CO)3]Br + 2 CO
This route avoids the formation of the tetraethylammonium bromide byproduct when the tetraethylammonium complex is used. This is desirable because the tetraethylammonium bromide is often difficult to remove from reaction mixtures.[5]
References
- ↑ Steven P. Schmidt; William C. Trogler; Fred Basolo (1990). "Pentacarbonylrhenium Halides". Inorganic Syntheses. Inorganic Syntheses. 28: 154–159. doi:10.1002/9780470132593.ch42. ISBN 9780470132593.
- ↑ W. Hieber, Mitarbeitern, Hans Schulten (1939). "XXX. Mitteilung über Metallcarbonyle. Über Rhenium-Kohlenoxyd-Verbindungen". Zeitschrift für anorganische und allgemeine Chemie. 243 (2): 164–173. doi:10.1002/zaac.19392430205.
- ↑ Michael A. Urbancic; John R. Shapley (1990). "Pentacarbonylhydridorhenium". Inorganic Syntheses. Inorganic Syntheses. 28: 165–8. doi:10.1002/9780470132593.ch43. ISBN 9780470132593.
- ↑ R. Alberto; A Egli; U. Abram; K. Hegetschweiler; V. Gramlich & P. A. Schubiger (1994). "Synthesis and reactivity of [NEt4]2[ReBr3(CO)3]. Formation and structural characterization of the clusters [NEt4][Re3(µ3-OH)(µ-OH)3(CO)9] and [NEt4][Re2(µ-OH)3(CO)6] by alkaline titration". J. Chem. Soc., Dalton Trans. (19): 2815–2820. doi:10.1039/DT9940002815.
- ↑ N. Lazarova; S. James; J. Babich & J. Zubieta (2004). "A convenient synthesis, chemical characterization and reactivity of [Re(CO)3(H2O)3]Br: the crystal and molecular structure of [Re(CO)3(CH3CN)2Br]". Inorganic Chemistry Communications. 7 (9): 1023–1026. doi:10.1016/j.inoche.2004.07.006.