Tetrarhodium dodecacarbonyl

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Tetrarhodium dodecacarbonyl
Rh4(CO)12.png
Tetrarhodium-dodecacarbonyl-from-xtal-173K-3D-balls-A.png
Rh4(CO)12.jpg
Names
IUPAC name
tri-μ-carbonyl-1:2κ2C;1:3κ2C;2:3κ2C-nonacarbonyl- 1κ2C,2κ2C,3κ2C,4κ3C-[Td-(13)-Δ4-closo]-tetrarhodium(6 RhRh)
Other names
rhodium(0) carbonyl; rhodium carbonyl; rhodium dodecacarbonyl
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.039.232 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 243-171-9
PubChem CID
  • InChI=1S/12CO.4Rh/c12*1-2;;;;
    Key: LVGLLYVYRZMJIN-UHFFFAOYSA-N
  • [Rh-2]1235(C#[O+])(C#[O+])C(=O)[Rh-2]246(C#[O+])(C#[O+])C(=O)[Rh-2]34(C#[O+])(C#[O+])(C1=O)[Rh-3]56(C#[O+])(C#[O+])C#[O+]
Properties
Rh4(CO)12
Molar mass 747.743 g/mol
AppearanceRed crystals
Solubility Chlorocarbons, toluene, tetrahydrofuran
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H302, H312, H332
P261, P264, P270, P271, P280, P301+P312, P302+P352, P304+P312, P304+P340, P312, P322, P330, P363, P501
Related compounds
Other cations
Tetracobalt dodecacarbonyl, Tetrairidium dodecacarbonyl
Related compounds
Rhodium(III) chloride, Rh6(CO)16, Rh2(CO)4Cl2
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tetrarhodium dodecacarbonyl is the chemical compound with the formula Rh4(CO)12. This dark-red crystalline solid is the smallest binary rhodium carbonyl that can be handled as a solid under ambient conditions. It is used as a catalyst in organic synthesis.

Contents

Structure, synthesis, reactions

According to X-ray crystallography, Rh4(CO)12 features a tetrahedral array of four Rh atoms with nine terminal CO ligands and three bridging CO ligands. The structure can be expressed as Rh4(CO)9(µ-CO)3. [1]

Rh4(CO)12 is prepared by treatment of an aqueous solution of rhodium trichloride with activated copper metal under an atmosphere of CO. [2]

4 RhCl3(H2O)3  +   8 Cu   +   22 CO   Rh4(CO)12  +   2 CO2  +   8 Cu(CO)Cl   +   4 HCl   +   10 H2O

Alternatively, the compound can be prepared by treatment of a methanolic solution of RhCl3(H2O)3 with CO to afford H[RhCl2(CO)2], followed by carbonylation in the presence of sodium citrate. [1]

The cluster undergoes thermal substitution with phosphine ligands, L: [3]

Rh4(CO)12-n  +  n L    Rh4(CO)12-nLn  +  n CO

Tetrarhodium dodecacarbonyl quantitatively decomposes in boiling hexane to afford hexadecacarbonylhexarhodium: [4]

3 Rh4(CO)12 → 2 Rh6(CO)16 + 4 CO

Because of their relevance to hydroformylation catalysis, rhodium carbonyls have been systematically studied to a high degree. The instability of Rh2(CO)8 has been a source of curiosity. The analogous binary carbonyl of cobalt, Co2(CO)8, is well known. Solutions of Rh4(CO)12 under high pressures of CO convert to the dirhodium compound: [5]

Rh4(CO)12 + 4 CO → Rh2(CO)8

Unlike Co2(CO)8 which features bridging carbonyls, the main isomer of Rh2(CO)8 features only terminal CO ligands. The relative instability of Rh2(CO)8 is analogous to the tendency of Ru(CO)5 to convert to Ru3(CO)12.

Related Research Articles

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Wilkinson's catalyst is the common name for chloridotris(triphenylphosphine)rhodium(I), a coordination complex of rhodium with the formula [RhCl(PPh3)3], where 'Ph' denotes a phenyl group). It is a red-brown colored solid that is soluble in hydrocarbon solvents such as benzene, and more so in tetrahydrofuran or chlorinated solvents such as dichloromethane. The compound is widely used as a catalyst for hydrogenation of alkenes. It is named after chemist and Nobel laureate Sir Geoffrey Wilkinson, who first popularized its use.

<span class="mw-page-title-main">Rhodium(III) chloride</span> 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.

<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">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">Dicobalt octacarbonyl</span> Chemical compound

Dicobalt octacarbonyl is an organocobalt compound with composition Co2(CO)8. This metal carbonyl is used as a reagent and catalyst in organometallic chemistry and organic synthesis, and is central to much known organocobalt chemistry. It is the parent member of a family of hydroformylation catalysts. Each molecule consists of two cobalt atoms bound to eight carbon monoxide ligands, although multiple structural isomers are known. Some of the carbonyl ligands are labile.

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

Triosmium dodecacarbonyl is a chemical compound with the formula Os3(CO)12. This yellow-colored metal carbonyl cluster is an important precursor to organo-osmium compounds. Many of the advances in cluster chemistry have arisen from studies on derivatives of Os3(CO)12 and its lighter analogue Ru3(CO)12.

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

Triruthenium dodecacarbonyl is the chemical compound with the formula Ru3(CO)12. Classified as metal carbonyl cluster, it is a dark orange-colored solid that is soluble in nonpolar organic solvents. The compound serves as a precursor to other organoruthenium compounds.

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

Tetrairidium dodecacarbonyl is the chemical compound with the formula Ir4(CO)12. This tetrahedral cluster is the most common and most stable "binary" carbonyl of iridium. This air-stable species is only poorly soluble in organic solvents. It has been used to prepare bimetallic clusters and catalysts, e.g. for the water gas shift reaction, and reforming, but these studies are of purely academic interest.

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<span class="mw-page-title-main">Organoiridium chemistry</span>

Organoiridium chemistry is the chemistry of organometallic compounds containing an iridium-carbon chemical bond. Organoiridium compounds are relevant to many important processes including olefin hydrogenation and the industrial synthesis of acetic acid. They are also of great academic interest because of the diversity of the reactions and their relevance to the synthesis of fine chemicals.

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<span class="mw-page-title-main">Organorhodium chemistry</span>

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Rhodocene is a chemical compound with the formula [Rh(C5H5)2]. Each molecule contains an atom of rhodium bound between two planar aromatic systems of five carbon atoms known as cyclopentadienyl rings in a sandwich arrangement. It is an organometallic compound as it has (haptic) covalent rhodium–carbon bonds. The [Rh(C5H5)2] radical is found above 150 °C (302 °F) or when trapped by cooling to liquid nitrogen temperatures (−196 °C [−321 °F]). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.

<span class="mw-page-title-main">Tris(triphenylphosphine)rhodium carbonyl hydride</span> Chemical compound

Carbonyl hydrido tris(triphenylphosphine)rhodium(I) [Carbonyl(hydrido)tris(triphenylphosphane)rhodium(I)] is an organorhodium compound with the formula [RhH(CO)(PPh3)3] (Ph = C6H5). It is a yellow, benzene-soluble solid, which is used industrially for hydroformylation.

<span class="mw-page-title-main">Cyclooctadiene iridium chloride dimer</span> Chemical compound

Cyclooctadiene iridium chloride dimer is an organoiridium compound with the formula [Ir(μ2-Cl)(COD)]2, where COD is the diene 1,5-cyclooctadiene (C8H12). It is an orange-red solid that is soluble in organic solvents. The complex is used as a precursor to other iridium complexes, some of which are used in homogeneous catalysis. The solid is air-stable but its solutions degrade in air.

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Chlorobis(ethylene)rhodium dimer is an organorhodium compound with the formula Rh2Cl2(C2H4)4. It is a red-orange solid that is soluble in nonpolar organic solvents. The molecule consists of two bridging chloride ligands and four ethylene ligands. The ethylene ligands are labile and readily displaced even by other alkenes. A variety of homogeneous catalysts have been prepared from this complex.

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

Rhodium carbonyl chloride is an organorhodium compound with the formula Rh2Cl2(CO)4. It is a red-brown volatile solid that is soluble in nonpolar organic solvents. It is a precursor to other rhodium carbonyl complexes, some of which are useful in homogeneous catalysis.

<span class="mw-page-title-main">Pentamethylcyclopentadienyl rhodium dichloride dimer</span> Chemical compound

Pentamethylcyclopentadienyl rhodium dichloride dimer is an organometallic compound with the formula [(C5(CH3)5RhCl2)]2, commonly abbreviated [Cp*RhCl2]2 This dark red air-stable diamagnetic solid is a reagent in organometallic chemistry.

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

Methylidynetricobaltnonacarbonyl is the organocobalt compound with the formula HCCo3(CO)9. It is a metal carbonyl cluster that contains the methylidyne ligand. The compound has C3v point group symmetry. It is a purple, air-stable solid that is soluble in some organic solvents, but not in water.

<span class="mw-page-title-main">Dichlororuthenium tricarbonyl dimer</span> Chemical compound

Dichlororuthenium tricarbonyl dimer is an organoruthenium compound with the formula [RuCl2(CO)3]2. A yellow solid, the molecule features a pair of octahedral Ru centers bridged by a pair of chloride ligands. The complex is a common starting material in ruthenium chemistry.

References

  1. 1 2 Serp, P.; Kalck, P.; Feurer, R.; Morancho, R. (1998). "Tri-µ-carbonyl-nonacarbonyltetrarhodium". Inorganic Syntheses. 32: 284–287. doi:10.1002/9780470132630.ch45.
  2. S. Martinengo; G. Giordano; P. Chini (1990). "Tri-µ-carbonyl-nonacarbonyltetrarhodium". Inorganic Syntheses. 28: 242–245. doi:10.1002/9780470132593.ch62.
  3. Heaton, Brian T.; Longhetti, Luciano; Michael, D.; Mingos, P.; Briant, Clive E.; Minshall, Peter C.; Theobald, Brian R.C.; Garlaschelli, Luigi; Sartorelli, Ugo (1981). "Structural Studies of Rh4(CO)12 Derivatives in Solution and in the Solid State". Journal of Organometallic Chemistry. 213: 333–350. doi:10.1016/S0022-328X(00)93969-X.
  4. Tunik, S. P.; Vlasov, A. V.; Krivykh, V. V. (1977). "Acetonitrile-Substituted Derivatives of Rh6(CO)16 : Rh6(CO)16-x(NCMe)x (x = 1,2)". Inorganic Syntheses. 31: 239–244. doi:10.1002/9780470132623.ch37.
  5. Brown, D. T.; Eguchi, T.; Heaton, B. T.; Iggo, J. A.; Whyman, R. (1991). "High-pressure spectroscopic studies of reactions of the clusters [Rh4(CO)12–x{P(OPh)3}x] (x = 1–4) with carbon monoxide or syngas". Journal of the Chemical Society, Dalton Transactions : 677–683. doi:10.1039/DT9910000677.

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