Tetracobalt dodecacarbonyl

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Tetracobalt dodecacarbonyl
Tetrarhodium-dodecacarbonyl-from-xtal-173K-3D-balls-A.png
Names
Other names
cobalt dodecacarbonyl, cobalt carbonyl
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.037.951 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 241-763-1
PubChem CID
  • InChI=1S/12CO.4Co/c12*1-2;;;;
    Key: YMFAWOSEDSLYSZ-UHFFFAOYSA-N
  • [Co-2]1235(C#[O+])(C#[O+])C(=O)[Co-2]246(C#[O+])(C#[O+])C(=O)[Co-2]34(C#[O+])(C#[O+])(C1=O)[Co-3]56(C#[O+])(C#[O+])C#[O+]
Properties
Co4(CO)12
Molar mass 571.858 g/mol
Appearanceblack crystal
Density 2.09 g/cm3
Melting point decomposes at60 °C (140 °F; 333 K)
Hazards
GHS labelling:
GHS-pictogram-flamme.svg GHS-pictogram-silhouette.svg GHS-pictogram-pollu.svg
Warning
H228, H301, H317, H331, H351
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Tetracobalt dodecacarbonyl is the chemical compound with the formula Co4(CO)12. It is a black crystalline compound that is insoluble in water and easily oxidized by air. It is an example of a metal carbonyl cluster.

Synthesis and structure

This compound is synthesized by decarbonylation of Co2(CO)8.

2 Co2(CO)8 → Co4(CO)12 + 4 CO

The molecule consists of a tetrahedral Co4 core, but the molecular symmetry is C3v. Three carbonyl ligands are bridging ligands and nine are terminal. [1] The average Co-Co distance is 2.499 Å, the average C-O bond length is 1.133 Å, and the average Co-C-O angle is 177.5°. [2] [3]

Rh4(CO)12 adopts the same C3v structure but Ir4(CO)12 has perfect Td symmetry with no bridging CO ligands groups. [4] The Rh4 and Ir4 clusters are more thermally robust than that of the Co4 compound, reflecting the usual trend in the strengths of metal-metal bond for second and third row metals vs those for the first row metals. There has been disagreement between the theoretically predicted and experimental structure of tetracobalt dodecacarbonyl. [5] [4] [6]

Related Research Articles

<span class="mw-page-title-main">Inorganic chemistry</span> Field of chemistry

Inorganic chemistry deals with synthesis and behavior of inorganic and organometallic compounds. This field covers chemical compounds that are not carbon-based, which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.

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

Nickel carbonyl (IUPAC name: tetracarbonylnickel) is a nickel(0) organometallic compound with the formula Ni(CO)4. This colorless liquid is the principal carbonyl of nickel. It is an intermediate in the Mond process for producing very high-purity nickel and a reagent in organometallic chemistry, although the Mond Process has fallen out of common usage due to the health hazards in working with the compound. Nickel carbonyl is one of the most dangerous substances yet encountered in nickel chemistry due to its very high toxicity, compounded with high volatility and rapid skin absorption.

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

Chromium hexacarbonyl (IUPAC name: hexacarbonylchromium) is a chromium(0) organometallic compound with the formula Cr(CO)6. It is homoleptic complex, which means that all the ligands are identical. It is a white, 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">Bridging ligand</span> Ligand which connects two or more (usually metal) atoms in a coordination complex

In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually restricted to small ligands such as pseudohalides or to ligands that are specifically designed to link two metals.

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

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<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">Tetrarhodium dodecacarbonyl</span> Chemical compound

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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.

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

Hexadecacarbonylhexarhodium is a metal carbonyl cluster with the formula Rh6(CO)16. It exists as purple-brown crystals that are slightly soluble in dichloromethane and chloroform. It is the principal binary carbonyl of rhodium.

Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. While iron adopts oxidation states from Fe(−II) through to Fe(VII), Fe(IV) is the highest established oxidation state for organoiron species. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.

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

Organorhodium chemistry is the chemistry of organometallic compounds containing a rhodium-carbon chemical bond, and the study of rhodium and rhodium compounds as catalysts in organic reactions.

<span class="mw-page-title-main">Rhodocene</span> Organometallic chemical compound

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<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

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In chemistry, a metal carbonyl cluster is a compound that contains two or more metals linked in part by metal-metal bonds and containing carbon monoxide (CO) as the exclusive or predominant ligand. The area is a subfield of metal carbonyl chemistry, and many metal carbonyl clusters are in fact prepared from simple metal carbonyls. Simple examples include Fe2(CO)9, Fe3(CO)12, Mn2(CO)10. High nuclearity clusters include [Rh13(CO)24H3]2− and the stacked Pt3 triangules [Pt3n(CO)6n]2− (n = 2–6).

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References

  1. Chini, P. (1968). "The closed metal carbonyl clusters". Inorganica Chimica Acta . 2: 31–51. doi:10.1016/0073-8085(68)80013-0.
  2. Farrugia, L. J.; Braga, D.; Grepioni, F. (1999). "A structure redetermination of Co4(CO)12: evidence for dynamic disorder and the pathway of metal atom migration in the crystalline phase". Journal of Organometallic Chemistry . 573 (1–2): 60–66. doi:10.1016/S0022-328X(98)00879-1.
  3. Corradini, P. (1959). "Structure of tetracobaltdodecarbonyl". Journal of Chemical Physics . 31 (6): 1676–1677. Bibcode:1959JChPh..31.1676C. doi:10.1063/1.1730674.
  4. 1 2 Wei, C. H. (1969). "Structural analyses of tetracobalt dodecacarbonyl and tetrarhodium dodecacarbonyl. Crystallographic treatments of a disordered structure and a twinned composite". Inorganic Chemistry . 8 (11): 2384–2397. doi:10.1021/ic50081a030.
  5. Corradini, Paolo (1959). "Structure of tetracobaltdodecarbonyl". Journal of Chemical Physics . 31 (6): 1676–1677. Bibcode:1959JChPh..31.1676C. doi:10.1063/1.1730674.
  6. Farrugia, Louis J.; Braga, Dario; Grepioni, Fabrizia (1999). "A structure redetermination of Co4(CO)12: Evidence for dynamic disorder and the pathway of metal atom migration in the crystalline phase". Journal of Organometallic Chemistry . 573 (1–2): 60–66. doi:10.1016/S0022-328X(98)00879-1.