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Tetrarhodium dodecacarbonyl
IUPAC name
Other names rhodium(0) carbonyl; rhodium carbonyl; rhodium dodecacarbonyl
CAS number 19584-30-6
Molecular formula C12O12Rh4
Molar mass 747.743 g/mol
Appearance Red crystals
Solubility Chlorocarbons, toluene, tetrahydrofuran
Related compounds
Related compounds Rhodium(III) chloride, Rh6(CO)16, Rh2(CO)4Cl2
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Tetrarhodium dodecacarbonyl is the chemical compound with the formula Rh4(CO)12. This dark-red crystalline solid is the smallest stable binary rhodium carbonyl. It is used as a catalyst in organic synthesis.


Structure, synthesis, reactions

The structure of Rh4(CO)12 is described by 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.

It is prepared by treatment of an aqueous solution of rhodium trichloride with activated copper metal under an atmosphere of CO.[1]

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.[2]

The cluster undergoes thermal substitution with phosphorus ligands:

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

Related metal carbonyls

Because of their relevance to hydroformylation catalysis, the metal carbonyls has 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 Rh5(CO)12 under high pressures of CO do convert to the dirhodium compound:[3]

Rh4(CO)12 + 4 CO → 2 Rh2(CO)8

The relative instability of Rh2(CO)8 conforms with a general trend: Ru(CO)5 loses CO spontaneously to give Ru3(CO)12.


  1. ^ S. Martinengo, G. Giordano, P. Chini, G. W. Parshall, E. R Wonchoba (1990). Robert J. Angelico. ed. "Tri-µ-carbonyl-nonacarbonyltetrarhodium". Inorganic Syntheses 28: 242 – 245. doi:10.1002/9780470132593.ch62.  
  2. ^ Serp, P.; Kalck, P.; Feurer, R.; Morancho, R. (1998). Marcetta. Y. Darensbourg. ed. "Tri-µ-carbonyl-nonacarbonyltetrarhodium". Inorganic Syntheses 32: 284 – 287. doi:10.1002/9780470132630.ch45.  
  3. ^ 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.  

General reading

  • King, R. B., "Rhodium: Organometallic Chemistry" Encyclopedia of Inorganic Chemistry 1994, 7, 3494.


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