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Hexadecacarbonylhexarhodium

Chemical compound From Wikipedia, the free encyclopedia

Hexadecacarbonylhexarhodium
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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.[1] It is the principal binary carbonyl of rhodium.

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Discovery and synthesis

Rh6(CO)16 was first prepared by Walter Hieber in 1943 by carbonylation of RhCl3·3H2O at 80230 °C and 200 atm carbon monoxide with silver or copper as a halide acceptor. Hieber correctly formulated the compound as a binary carbonyl, but suggested the formula Rh4(CO)11, i.e., CO/Rh ratio of 2.75.[2] The correct formula and structure was subsequently established by Dahl et al. using X-ray crystallography. The correct CO/Rh ratio is 2.66.[3]

Relative to the original preparation, the carbonylation of a mixture of anhydrous rhodium trichloride and iron pentacarbonyl was shown to give good yields of Rh6(CO)16.[4] Other compounds of rhodium are also effective precursors such as [(CO)2Rh(μ-Cl)]2 and rhodium(II) acetate:[1]

3 Rh2(O2CCH3)4 + 22 CO + 6 H2O  Rh6(CO)16 +  6 CO2 + 12 CH3COOH
3 [(CO)2RhCl]2 + 4 CO + 6 Cu  Rh6(CO)16 + 6 CuCl

It also arises quantitatively by thermal decomposition of tetrarhodium dodecacarbonyl in boiling hexane:[5]

3 Rh4(CO)12 → 2 Rh6(CO)16 + 4 CO
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Reactions

At least some of the CO ligands can be displaced by donor ligands.[5]

Rh6(CO)16 catalyzes a number of organic reactions including hydrogenation and hydroformylation.[4]

References

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