Metal carbonyl cluster

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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. [1] High nuclearity clusters include [Rh13(CO)24H3]2− and the stacked Pt3 triangules [Pt3n(CO)6n]2− (n = 2–6). [2]

Contents

Structure of Rh4(CO)12. Tetrarhodium-dodecacarbonyl-from-xtal-173K-3D-balls-A.png
Structure of Rh4(CO)12.

History

The first metal carbonyl clusters, Fe3(CO)12, Ir4(CO)12, and Rh6(CO)16, were reported starting in the 1930s, often by Walter Hieber. [3] [4] The structures were subsequently established by X-ray crystallography.. [5]

Paolo Chini (1928–1980) was a pioneer for the synthesis and characterization of high nuclearity metal carbonyl clusters. His first studies started in 1958, in the attempt to repeat a patent that claimed an improved selectivity in hydroformylation. From a mixture of iron and cobalt carbonyls the first bimetallic carbonyl cluster HFeCo3(CO)12 was obtained. [6]

Classes of carbonyl clusters

Binary metal carbonyl clusters

Binary carbonyl clusters consist only of metal and CO. They are the most widely studied and used metal carbonyl clusters. They arise in general by the condensation of unsaturated metal carbonyls. Dissociation of CO from Ru(CO)5 would give Ru(CO)4, which could trimerize to Ru3(CO)12. The reaction mechanisms are more complicated than this simple scenario. Condensation of low molecular weight metal carbonyls requires decarbonylation, which can be induced thermally, photochemically, or using various reagents. The nuclearity (number of metal centers) of binary metal carbonyl clusters is usually no greater than six.

metalparent carbonylcluster
Fe Fe(CO)5 Fe2(CO)9, Fe3(CO)12
RuRu(CO)5 Ru3(CO)12
OsOs(CO)5 Os3(CO)12
Co Co2(CO)8 Co4(CO)12
RhRh2(CO)8 Rh4(CO)12
IrIr2(CO)8 Ir4(CO)12

"Chini clusters"

The synthesis and characterization of the platinum carbonyl dianions [Pt3n(CO)6n]2- (n = 1-10), also known as Chini clusters or more correctly Chini-Longoni clusters, are recognized by the scientific community as the most spectacular result of Chini's work. [7]

Chini clusters follow the general formula of [Pt3(CO)6]n2−, 1 < n < 10. [8] These clusters are prepared by reduction of hexachloroplatinate with strongly basic methanol under an atmosphere of CO. [9] These clusters consist of stacks of triangularly shaped Pt3 subunits. Although these clusters were first reported in 1969 by Chatt and Booth, their structure were not established until Chini and Longoni's work in 1976. [8] [9]

Platinum Carbonyl Cluster Moteiff AKA Chini Cluster.jpg

Chini clusters are based on a planar triangular building block that can be condensed as multiple units forming chains usually anywhere from two to ten units long. The chains are formed by stacking of the planar units, extending through platinum to platinum bonds forming trigonal prismatic clusters. Within a triangular unit, the platinum-platinum bond lengths are 2.65 Å and between units the Pt---Pt bond lengths are 3.05 Å. Cluster structure is easily disrupted by deposition onto surfaces such as carbon or silicon, where the chains are broken, but the triangular subunits remain intact. [10] The tetramer [Pt3(CO)6]42− is the most common member of this series of clusters. [11] These clusters undergo reversible redox. They catalyze the hydrogenation of alkenes, ketones, and aldehydes.

Chini clusters can also be converted heterometal clusters and catalyze pH driven redox reactions and transport. First, the Chini clusters are the source of platinum atoms for the mixed metal cluster synthesis. [8] For instance, the reaction [Pt12(CO)24]2− with [Ag(PPh3)4]+ produces heterometal cluster [Pt3Ag(CO)3(PPh3)5]+. Second, the Chini clusters with redox properties act as a catalyst that helps transport sodium ions and electrons in the same direction across a liquid membrane, driven by pH-gradient. The [Pt3(CO)6]n-12− platinum clusters, where n = 4 – 6, are reduced by OH−:

(n-1)[Pt3(CO)6]n2− + 2OH− ↔ n[Pt3(CO)6]n-12− + H2O + 1/2O2

Metal carbido clusters

The carbido cluster [Os10C(CO)24] . The bent OsCO units are an artifact of the crystallographic analysis. Os10(CO)24 2-.png
The carbido cluster [Os10C(CO)24] . The bent OsCO units are an artifact of the crystallographic analysis.

Although the nuclearity of binary metal carbonyl clusters is usually six or fewer, carbido clusters often have higher nuclearities. Metal carbonyls of the iron and cobalt triads are well known to form carbido derivatives. Examples include [Rh6C(CO)15]2− [13] and [Ru6C(CO)16]2−. [14] Carbonyl carbides exist not only with fully encapsulated carbon (e.g., [Fe6C(CO)16]2−) but also with exposed carbon centres as in Fe5C(CO)15 and Fe4C(CO)13. [15]

Bonding

For low nuclearity clusters, bonding is often described as if it is localized. For this purpose, the eighteen electron rule is used. Thus, 34 electrons in an organometallic complex predicts a dimetallic complex with a metal-metal bond. For higher nuclearity clusters, more elaborate rules are invoked including Jemmis mno rules and Polyhedral skeletal electron pair theory.

Although clusters are often written with discrete M-M bonds, the nature of this bonding is unclear, especially when there are bridging ligands. [16]

Related Research Articles

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<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

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<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">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">Tetrarhodium dodecacarbonyl</span> Chemical compound

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.

Transition metal hydrides are chemical compounds containing a transition metal bonded to hydrogen. Most transition metals form hydride complexes and some are significant in various catalytic and synthetic reactions. The term "hydride" is used loosely: some of them are acidic (e.g., H2Fe(CO)4), whereas some others are hydridic, having H−-like character (e.g., ZnH2).

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<span class="mw-page-title-main">Tetrabutylammonium</span> Polyatomic ion (N(C₄H₉)₄, charge +1)

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<span class="mw-page-title-main">Paolo Chini</span> Italian chemist

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Metal cluster compounds are a molecular ion or neutral compound composed of three or more metals and featuring significant metal-metal interactions.

References

  1. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  2. ↑ Paul J. Dyson, J. Scott McIndoe "Transition Metal Carbonyl Cluster Chemistry" Taylor & Francis, 2000.
  3. ↑ Hieber, W.; Lagally, H. (1940). "Über Metallcarbonyle. XXXV. Über Iridiumcarbonyl". Zeitschrift für Anorganische und Allgemeine Chemie. 245 (3): 321–333. doi:10.1002/zaac.19402450311.
  4. ↑ Hieber, W.; Lagally, H. (1943). "Über Metallcarbonyle. XLV. Das Rhodium im System der Metallcarbonyle". Zeitschrift für Anorganische und Allgemeine Chemie. 251 (1): 96–113. doi:10.1002/zaac.19432510110.
  5. ↑ Corey, Eugene R.; Dahl, Lawrence F.; Beck, Wolfgang (1963). "Rh6(CO)16 and its Identity with Previously Reported Rh4(CO)11". J. Am. Chem. Soc. 85 (8): 1202–1203. doi:10.1021/ja00891a040.
  6. ↑ Paolieri, Matteo; Ciabatti, Iacopo; Fontani, Marco (2019). "Paolo Chini: The Chemical Architect of Metal Carbonyl Clusters". Journal of Cluster Science. 30 (6): 1623–1631. doi:10.1007/s10876-019-01607-7. S2CID   191176974.
  7. ↑ Paolieri, Matteo; Ciabatti, Iacopo; Fontani, Marco (2019). "Paolo Chini: The Chemical Architect of Metal Carbonyl Clusters". Journal of Cluster Science. 30 (6): 1623–1631. doi:10.1007/s10876-019-01607-7. S2CID   191176974.
  8. 1 2 3 Bhaduri, S.; Sharma, K.; Mukesh, D. Proc. Indian Acad. Sci. 1994, 713-716.
  9. 1 2 Bhaduri ,S. Current Science, 2000, 78(11), 1318-1324
  10. ↑ Calabrese, J. C.; Dahl, L. F.; Chini, P.; Longoni, G.; Martinengo, S. J. Am. Chem. Soc., 1974, 96 (8), pp 2614–2616
  11. ↑ Treguer, M.; Remita, H.; Pernot, P.; Khatouri, J.; Belloni, J. J. Phys. Chem. A2001, 105, 6102.
  12. ↑ Jackson, P. F., Johnson, B. F. G., Lewis, J., Nelson, W. J. H., McPartlin, M., "The synthesis of the cluster dianion [Os10C(CO)24]2- by pyrolysis. X-Ray structure analysis of [N(PPh3)2]2[Os10C(CO)24] and [Os5C(CO)14H(NC5H4)]", Journal of the Chemical Society, Dalton Transactions 1982, 2099. doi : 10.1039/DT9820002099
  13. ↑ S. Martinengo, D. Strumolo, P. Chini, "Dipotassium μ6-Carbido-Nona-μ-Carbonyl-Hexacarbonylhexarhodate(2-) K2[Rh6(CO)6(μ-CO)9-μ-C]" Inorganic Syntheses, 1980, Volume 20, Pages: 212–215, 2007. doi : 10.1002/9780470132517.ch48
  14. ↑ Elena Cariati, Claudia Dragonetti, Elena Lucenti, Dominique Roberto, "Tri- and Hexaruthnium Carbonyl Clusters" Inorganic Syntheses, 2004, Volume 35, 210.
  15. ↑ Ernestine W. Hill, John S. Bradley, "Tetrairon Carbido Carbonyl Clusters" Inorganic Syntheses, 1990, Volume 27, Pages: 182–188. doi : 10.1002/9780470132586.ch36
  16. ↑ Jennifer C. Green, Malcolm L. H. Green, Gerard Parkin "The occurrence and representation of three-centre two-electron bonds in covalent inorganic compounds" Chem. Commun. 2012, 11481-11503. doi : 10.1039/c2cc35304k
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