Dirhenium decacarbonyl

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Dirhenium decacarbonyl
Re2(CO)10improved.svg
Rhenium-carbonyl-3D-balls.png
Re2(CO)10 sample.JPG
Names
IUPAC name
bis(pentacarbonylrhenium)(ReRe)
Other names
Rhenium carbonyl; rhenium pentacarbonyl
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.034.714 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 238-202-8
PubChem CID
  • InChI=1S/10CO.2Re/c10*1-2;; Yes check.svgY
    Key: ZIZHEHXAMPQGEK-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/10CO.2Re/c10*1-2;;
    Key: ZIZHEHXAMPQGEK-UHFFFAOYAX
  • [Re].[Re].[C-]#[O+].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-]
Properties
Re2(CO)10
Molar mass 652.52 g/mol
Melting point 170 °C (338 °F; 443 K) (decomposes)
Hazards [1]
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-exclam.svg
Danger
H301, H330, H331, H332
P261, P271, P304+P340+P311, P403+P233, P405, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

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. [2] 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. [3]

Contents

History

In the 1930s Robert Mond developed methods which used increased pressure and temperature to produce various forms of metal carbonyl . A prominent scientist of the twentieth century, Walter Hieber was crucial to the further development of specifically the dirhenium decacarbonyl. Initial efforts produced mononuclear metal complexes, but upon further evaluation, Hieber discovered that by using Re2O7 as a starting material with no solvent, a dirhenium complex could be achieved producing a Re-Re interaction. [4]

Structure and properties

The crystal structure of Re2(CO)10 is relatively well known. The compound consists of a pair of square pyramidal Re(CO)5 units linked by a Re-Re bond. There are two different conformations that can occur: staggered and eclipsed. The eclipsed conformation occurs about 30% of the time, producing a D4h point group, but the staggered form, with point group D4d, is more stable. The Re-Re bond length was experimentally found to be 3.04Å. [5]

The Re atom exists in a slightly distorted octahedral configuration with the C axial-Re-C equatorial angle equal to 88°. The mean Re-C bond length of 2.01 Å is the same for the axial and equatorial positions. The mean C-O distance is 1.16 Å. [2] [6]

This compound has a broad IR absorption band at 1800 cm−1 region can be assigned to two components centered at 1780 and 1830 cm−1, resulting from CO adsorption. The remaining nine CO groups in Re2(CO)10 give the complex IR absorption in the 1950–2150 cm−1 region. Free Re2(CO)10 (point symmetry D4d ) has a CO stretch representation of 2A1+E2 + E3+ 2B2 +E1, where 2B2 + E1 are IR active. For an axially perturbed (C4v) Re2(CO)10 molecule, the CO stretch representation was found to be 2E+B1+B2+3A1, where the IR active modes are 2E+3A1. [7]

Its identity can also be confirmed by mass spectrometry, using the isotopic pattern of rhenium (185Re and 187Re). [8]

Synthesis

Dirhenium decacarbonyl may be obtained by reductive carbonylation of rhenium(VII) oxide (Re2O7) at 350 atm and 250 °C. [4]

Re2O7 + 17 CO → Re2(CO)10 + 7 CO2

It can also be prepared by the reaction of a methanol solution of sodium perrhenate and carbon monoxide at 230 °C and 115 atm. [9]

Reactions

The carbonyl ligands may be displaced by other ligands such as phosphines and phosphites (denoted L). [8] [10]

Re2(CO)10 + 2 L → Re2(CO)8L2

This compound may also be "cracked" to mononuclear Re(I) carbonyl complexes by halogenation: [11]

Re2(CO)10 + X2 → 2 Re(CO)5X (X = Cl, Br, I)

When bromine is used, bromopentacarbonylrhenium(I) is formed, which is an intermediate for many more rhenium complexes. [8] This compound may also be hydrogenated to form various polyrhenium complexes, eventually giving elemental rhenium. [12]

Re2(CO)10 → H3Re3(CO)12 → H5Re4(CO)12 → Re (metal)

In the presence of water, photolysis of Re2(CO)10 yields a hydroxide complex: [13]

Re2(CO)10 → HRe(CO)5 + Re4(CO)12(OH)4

This reaction includes the cleavage of Re-Re bond and the synthesis of HRe(CO)5, which can be used to prepare surface structures designed to incorporate isolated surface-bound Re carbonyl complexes. [14]

Loss of a carbonyl ligand by photolysis generates a coordinatively unsaturated complex that undergoes oxidative addition of Si-H bonds, for example:

Re2(CO)10 + HSiCl3* → (CO)5ReHRe(CO)4SiCl3 + CO

Applications

Rhenium-based catalysis have been used in metathesis, reforming, hydrogenation and various hydrotreating processes such as hydrodesulfurization. [15] Re2(CO)10 can be used to promote the silation of alcohols and prepare the silyl ethers, and its reaction: [16]

RSiH3 + R'OH → RH2SiOR' + H2.

See also

Related Research Articles

<span class="mw-page-title-main">Rhenium</span> Chemical element, symbol Re and atomic number 75

Rhenium is a chemical element; it has 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. It has the third-highest melting point and second-highest boiling point of any element at 5869 K. It resembles manganese and technetium chemically and is mainly obtained as a by-product of the extraction and refinement of molybdenum and copper ores. It shows in its compounds a wide variety of oxidation states ranging from −1 to +7.

<span class="mw-page-title-main">Group 7 element</span> Group of chemical elements

Group 7, numbered by IUPAC nomenclature, is a group of elements in the periodic table. It contains manganese (Mn), technetium (Tc), rhenium (Re) and bohrium (Bh). This group lies in the d-block of the periodic table, and are hence transition metals. This group is sometimes called the manganese group or manganese family after its lightest member; however, the group itself has not acquired a trivial name because it belongs to the broader grouping of the transition metals.

<span class="mw-page-title-main">Perrhenic acid</span> Chemical compound

Perrhenic acid is the chemical compound with the formula Re2O7(H2O)2. It is obtained by evaporating aqueous solutions of Re2O7. Conventionally, perrhenic acid is considered to have the formula HReO4, and a species of this formula forms when rhenium(VII) oxide sublimes in the presence of water or steam. When a solution of Re2O7 is kept for a period of months, it breaks down and crystals of HReO4·H2O are formed, which contain tetrahedral ReO−4. For most purposes, perrhenic acid and rhenium(VII) oxide are used interchangeably. Rhenium can be dissolved in nitric or concentrated sulfuric acid to produce perrhenic acid.

<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">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Rhenium(VII) oxide</span> Chemical compound

Rhenium(VII) oxide is the inorganic compound with the formula Re2O7. This yellowish solid is the anhydride of HOReO3. Perrhenic acid, Re2O7·2H2O, is closely related to Re2O7. Re2O7 is the raw material for all rhenium compounds, being the volatile fraction obtained upon roasting the host ore.

<span class="mw-page-title-main">Triiron dodecacarbonyl</span> Chemical compound

Triiron dodecarbonyl is the organoiron compound with the formula Fe3(CO)12. It is a dark green solid that sublimes under vacuum. It is soluble in nonpolar organic solvents to give intensely green solutions. Most low-nuclearity clusters are pale yellow or orange. Hot solutions of Fe3(CO)12 decompose to an iron mirror, which can be pyrophoric in air.The solid decomposes slowly in air, and thus samples are typically stored cold under an inert atmosphere. It is a more reactive source of iron(0) than iron pentacarbonyl.

<span class="mw-page-title-main">Dimanganese decacarbonyl</span> Chemical compound

Dimanganese decacarbonyl, which has the chemical formula Mn2(CO)10, is a binary bimetallic carbonyl complex centered around the first row transition metal manganese. The first reported synthesis of Mn2(CO)10 was in 1954 at Linde Air Products Company and was performed by Brimm, Lynch, and Sesny. Their hypothesis about, and synthesis of, dimanganese decacarbonyl was fundamentally guided by the previously known dirhenium decacarbonyl (Re2(CO)10), the heavy atom analogue of Mn2(CO)10. Since its first synthesis, Mn2(CO)10 has been use sparingly as a reagent in the synthesis of other chemical species, but has found the most use as a simple system on which to study fundamental chemical and physical phenomena, most notably, the metal-metal bond. Dimanganese decacarbonyl is also used as a classic example to reinforce fundamental topics in organometallic chemistry like d-electron count, the 18-electron rule, oxidation state, valency, and the isolobal analogy.

Walter Hieber was an inorganic chemist, known as the father of metal carbonyl chemistry. He was born 18 December 1895 and died 29 November 1976. Hieber's father was Johannes Hieber, an influential evangelical minister and politician.

<span class="mw-page-title-main">Bromopentacarbonylrhenium(I)</span> Chemical compound

Bromopentacarbonylrhenium(I) is an inorganic compound of rhenium, commonly used for the syntheses of other rhenium complexes.

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.

<span class="mw-page-title-main">Cobalt tetracarbonyl hydride</span> Chemical compound

Cobalt tetracarbonyl hydride is an organometallic compound with the formula HCo(CO)4. It is a volatile, yellow liquid that forms a colorless vapor and has an intolerable odor. The compound readily decomposes upon melt and in absentia of high CO partial pressures forms Co2(CO)8. Despite operational challenges associated with its handling, the compound has received considerable attention for its ability to function as a catalyst in hydroformylation. In this respect, HCo(CO)4 and related derivatives have received significant academic interest for their ability to mediate a variety of carbonylation (introduction of CO into inorganic compounds) reactions.

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

Pentacarbonylhydridomanganese is an organometallic compound with formula HMn(CO)5. This compound is one of the most stable "first-row" transition metal hydrides.

<span class="mw-page-title-main">Iron tetracarbonyl dihydride</span> Chemical compound

Iron tetracarbonyl dihydride is the organometallic compound with the formula H2Fe(CO)4. This compound was the first transition metal hydride discovered. The complex is stable at low temperatures but decomposes rapidly at temperatures above –20 °C.

<span class="mw-page-title-main">Tolman electronic parameter</span>

The Tolman electronic parameter (TEP) is a measure of the electron donating or withdrawing ability of a ligand. It is determined by measuring the frequency of the A1 C-O vibrational mode (ν(CO)) of a (pseudo)-C3v symmetric complex, [LNi(CO)3] by infrared spectroscopy, where L is the ligand of interest. [LNi(CO)3] was chosen as the model compound because such complexes are readily prepared from tetracarbonylnickel(0). The shift in ν(CO) is used to infer the electronic properties of a ligand, which can aid in understanding its behavior in other complexes. The analysis was introduced by Chadwick A. Tolman.

<span class="mw-page-title-main">Cyclopentadienyliron dicarbonyl dimer</span> Chemical compound

Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).

<span class="mw-page-title-main">Metal carbonyl hydride</span>

Metal carbonyl hydrides are complexes of transition metals with carbon monoxide and hydride as ligands. These complexes are useful in organic synthesis as catalysts in homogeneous catalysis, such as hydroformylation.

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

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

Transition metal acyl complexes describes organometallic complexes containing one or more acyl (RCO) ligands. Such compounds occur as transient intermediates in many industrially useful reactions, especially carbonylations.

Rhenium compounds are compounds formed by the transition metal rhenium (Re). Rhenium can form in many oxidation states, and compounds are known for every oxidation state from -3 to +7 except -2, although the oxidation states +7, +4, and +3 are the most common. Rhenium is most available commercially as salts of perrhenate, including sodium and ammonium perrhenates. These are white, water-soluble compounds. The tetrathioperrhenate anion [ReS4] is possible.

References

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  3. F. Armstrong; J. Rourke; M. Hagerman; M. Weller; P. Atkins; T. Overton (2010). "Shiver and Atkins' Inorganic Chemistry 5th edition": 555.{{cite journal}}: Cite journal requires |journal= (help)
  4. 1 2 H. Werner (2009). "Organo-Transition Metal Chemistry: A personal View" : 93.{{cite journal}}: Cite journal requires |journal= (help)
  5. M. Churchill; K. Amoh; H. Wasserman (1981). "Redetermination of the crystal structure of dimanganese decacarbonyl and determination of the crystal structure of dirhenium decacarbonyl. Revised values for the manganese-manganese and rhenium-rhenium bond lengths in dimanganese decacarbonyl and dirhenium decacarbonyl". Inorganic Chemistry . 20 (3): 1609–1612. doi:10.1021/ic50219a056.
  6. N.IGapotchenko; et al. (1972). "Molecular structure of dirhenium decacarbonyl". Journal of Organometallic Chemistry . 35 (2): 319–320. doi:10.1016/S0022-328X(00)89806-X.
  7. E. Escalona Platero; F.R. Peralta; C. Otero Areán (1995). "Vapour phase deposition and thermal decarbonylation of Re2(CO)10 on gamma-alumina: infrared studies". Catalysis Letters . 34 (1): 65–73. doi:10.1007/BF00808323. S2CID   101025211.
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  9. Crocker, Lisa S.; Gould, George L.; Heinekey, D. Michael (1988). "Improved Synthesis of Carbonylrhenium". Journal of Organometallic Chemistry. 342 (2): 243–244. doi:10.1016/s0022-328x(00)99461-0.
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  11. Steven P. Schmidt; William C. Trogler; Fred Basolo (2007). Pentacarbonylrhenium Halides. Inorganic Syntheses. Vol. 28. pp. 154–159. doi:10.1002/9780470132593.ch42. ISBN   9780470132593.
  12. C. Dossi, J. Schaefer, W. M. H. Sachtler (1989). "Mechanism of particle formation in decomposing Re2(CO)10 on NaY and NaHY zeolites: effect of prereduced Pt clusters in the supercages". Journal of Molecular Catalysis. 52 (1): 193–209. doi:10.1016/0304-5102(89)80089-6.{{cite journal}}: CS1 maint: multiple names: authors list (link)
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  14. P. S. Kirlin; et al. (1990). "Surface catalytic sites prepared from [HRe(CO)5] and [H3Re3(CO)12]: mononuclear, trinuclear, and metallic rhenium catalysts supported on magnesia". Journal of Physical Chemistry . 94 (92): 8439–8450. doi:10.1021/j100385a017. hdl:1874/5964. S2CID   55214603.
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