Bromopentacarbonylrhenium(I)

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Bromopentacarbonylrhenium(I)
Bromopentacarbonylrhenium(I)-3D-balls.png
Names
IUPAC name
Bromidopentacarbonylrhenium
Identifiers
3D model (JSmol)
ECHA InfoCard 100.034.607 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 238-084-8
PubChem CID
  • InChI=1S/5CO.BrH.Re/c5*1-2;;/h;;;;;1H;/q;;;;;;+1/p-1
    Key: NWJBOTGGBYFKEJ-UHFFFAOYSA-M
  • [C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].Br[Re]
Properties
Re(CO)5Br
Molar mass 406.16 g/mol
Appearancecolorless
Melting point sublimes 85-90 °C (0.2 mm Hg)
Solubility in chlorocarbonssoluble
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H301, H311, H315, H319, H331, H335
P261, P264, P270, P271, P280, P301+P310, P302+P352, P304+P340, P305+P351+P338, P311, P312, P321, P322, P330, P332+P313, P337+P313, P361, P362, P363, P403+P233, P405, P501
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.

Contents

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 precursor to other rhenium complexes. It reacts with zinc and acetic acid to give pentacarbonylhydridorhenium (HRe(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]

Heating bromopentacarbonylrhenium(I) in water give the triaquo complex:

ReBr(CO)5 + 3 H2O → [Re(H2O)3(CO)3]Br + 2 CO

This route avoids the formation of the tetraethylammonium bromide byproduct, which is often difficult to remove from reaction mixtures. [5]

Related Research Articles

Rhenium Chemical element, symbol Re and atomic number 75

Rhenium is a chemical element with the symbol Re and atomic number 75. It is a silvery-gray, heavy, third-row transition metal in group 7 of the periodic table. With an estimated average concentration of 1 part per billion (ppb), rhenium is one of the rarest elements in the Earth's crust. Rhenium has the third-highest melting point and highest boiling point of any stable element at 5869 K. Rhenium resembles manganese and technetium chemically and is mainly obtained as a by-product of the extraction and refinement of molybdenum and copper ores. Rhenium shows in its compounds a wide variety of oxidation states ranging from −1 to +7.

Triphenylphosphine Chemical compound

Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to PPh3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists as relatively air stable, colorless crystals at room temperature. It dissolves in non-polar organic solvents such as benzene and diethyl ether.

Rhodium(III) chloride Chemical compound

Rhodium(III) chloride refers to inorganic compounds with the formula RhCl3(H2O)n, where n varies from 0 to 3. These are diamagnetic solids featuring octahedral Rh(III) centres. Depending on the value of n, the material is either a dense brown solid or a soluble reddish salt. The soluble trihydrated (n = 3) salt is widely used to prepare compounds used in homogeneous catalysis, notably for the industrial production of acetic acid and hydroformylation.

Ruthenium(III) chloride Chemical compound

Ruthenium(III) chloride is the chemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.

Molybdenum(V) chloride Chemical compound

Molybdenum(V) chloride is the inorganic compound with the formula [MoCl5]2. This dark volatile solid is used in research to prepare other molybdenum compounds. It is moisture-sensitive and soluble in chlorinated solvents. Usually called molybdenum pentachloride, it is in fact a dimer with the formula Mo2Cl10.

Organomercury Group of chemical compounds containing mercury

Organomercury refers to the group of organometallic compounds that contain mercury. Typically the Hg–C bond is stable toward air and moisture but sensitive to light. Important organomercury compounds are the methylmercury(II) cation, CH3Hg+; ethylmercury(II) cation, C2H5Hg+; dimethylmercury, (CH3)2Hg, diethylmercury, and merbromin ("Mercurochrome"). Thiomersal is used as a preservative for vaccines and intravenous drugs.

Tantalum(V) bromide Chemical compound

Tantalum(V) bromide is the inorganic compound with the formula Taa2Br10. Its name comes from the compound's empirical formula, TaBr5. It is a diamagnetic, orange solid that hydrolyses readily. The compound adopts an edge-shared bioctahedral structure, which means that two TaBr5 units are joined by a pair of bromide bridges. There is no bond between the Ta centres. Niobium(V) chloride, niobium(V) bromide, niobium(V) iodide, tantalum(V) chloride, and tantalum(V) iodide all share this structural motif.

Iron(II) bromide Chemical compound

Iron(II) bromide is an inorganic compound with the chemical formula FeBr2. The anhydrous compound is a yellow or brownish-colored paramagnetic solid. Several hydrates of FeBr2 are also known, all being pale colored solids. It is a common precursor to other iron compounds in research laboratory, but no applications exist for this compound.

Trimethylphosphine Chemical compound

Trimethylphosphine is a neutral organophosphorus compound with the formula P(CH3)3, commonly abbreviated as PMe3. This colorless liquid has a strongly unpleasant odor, characteristic of alkylphosphines. The compound is a common ligand in coordination chemistry.

Pentacarbonylhydridorhenium Chemical compound

Pentacarbonylhydridorhenium is a chemical compound with the formula ReH(CO)5. This colorless liquid is a weak acid and represents one of the most important derivatives of dirhenium decacarbonyl (Re2(CO)10). It is synthesized by treating a methanolic solution of bromopentacarbonylrhenium(I) (Re(CO)5Br) with zinc and acetic acid (HOAc).

Cyclooctadiene rhodium chloride dimer Chemical compound

Cyclooctadiene rhodium chloride dimer is the organorhodium compound with the formula Rh2Cl2(C8H12)2, commonly abbreviated [RhCl(COD)]2 or Rh2Cl2(COD)2. This yellow-orange, air-stable compound is a widely used precursor to homogeneous catalysts.

Trirhenium nonachloride Chemical compound

Trirhenium nonachloride is a compound with the formula ReCl3, sometimes also written Re3Cl9. It is a dark red hygroscopic solid that is insoluble in ordinary solvents. The compound is important in the history of inorganic chemistry as an early example of a cluster compound with metal-metal bonds. It is used as a starting material for synthesis of other rhenium complexes.

Dirhenium decacarbonyl Chemical compound

Dirhenium decacarbonyl is the inorganic compound with the chemical formula Re2(CO)10. Commercially available, it is used as a starting point for the synthesis of many rhenium carbonyl complexes. It was first reported in 1941 by Walter Hieber, who prepared it by reductive carbonylation of rhenium. The compound consists of a pair of square pyramidal Re(CO)5 units joined via a Re-Re bond, which produces a homoleptic carbonyl complex.

Cobalt(II) bromide Chemical compound

Cobalt(II) bromide (CoBr2) is an inorganic compound. In its anhydrous form, it is a green solid that is soluble in water, used primarily as a catalyst in some processes.

The perrhenate ion is the anion with the formula ReO
4
, or a compound containing this ion. The perrhenate anion is tetrahedral, being similar in size and shape to perchlorate and the valence isoelectronic permanganate. The perrhenate anion is stable over a broad pH range and can be precipitated from solutions with the use of organic cations. At normal pH, perrhenate exists as metaperrhenate, but at high pH mesoperrhenate forms. Perrhenate, like its conjugate acid perrhenic acid, features rhenium in the oxidation state of +7 with a d0 configuration. Solid perrhenate salts takes on the color of the cation.

Organorhenium chemistry describes the compounds with Re−C bonds. Because rhenium is a rare element, relatively few applications exist, but the area has been a rich source of concepts and a few useful catalysts.

Metal halides

Metal halides are compounds between metals and halogens. Some, such as sodium chloride are ionic, while others are covalently bonded. A few metal halides are discrete molecules, such as uranium hexafluoride, but most adopt polymeric structures, such as palladium chloride.

Tetrabutylammonium Ion

Tetrabutylammonium is a quaternary ammonium cation with the formula [N(C4H9)4]+. It is used in the research laboratory to prepare lipophilic salts of inorganic anions. Relative to tetraethylammonium derivatives, tetrabutylammonium salts are more lipophilic but crystallize less readily.

Transition metal nitrile complexes Class of coordination compounds containing nitrile ligands (coordinating via N)

Transition metal nitrile complexes are coordination compounds containing nitrile ligands. Because nitriles are weakly basic, the nitrile ligands in these complexes are often labile.

Transition metal chloride complex 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.

References

  1. Steven P. Schmidt; William C. Trogler; Fred Basolo (1990). Pentacarbonylrhenium Halides. Inorganic Syntheses. Vol. 28. pp. 154–159. doi:10.1002/9780470132593.ch42. ISBN   9780470132593.
  2. W. Hieber; 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.
  3. Michael A. Urbancic; John R. Shapley (1990). Pentacarbonylhydridorhenium. Inorganic Syntheses. Vol. 28. pp. 165–8. doi:10.1002/9780470132593.ch43. ISBN   9780470132593.
  4. 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][Re33-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.
  5. 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.