Hexadecacarbonylhexarhodium

Hexadecacarbonylhexarhodium
Names
	IUPAC name Hexadecacarbonylhexarhodium
	Other names Hexarhodium hexadecacarbonyl
Identifiers
CAS Number	28407-51-4 [ECHA];
3D model (JSmol)	Interactive image;
ChemSpider	9041327;
ECHA InfoCard	100.044.539
EC Number	249-009-3;
PubChem CID	10866043;
CompTox Dashboard (EPA)	DTXSID10951074 ;
	InChI InChI=1S/16CO.6Rh/c16*1-2;;;;;; Key: SZQABOJVTZVBHE-UHFFFAOYSA-N;
	SMILES [C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[C-]#[O+].[Rh].[Rh].[Rh].[Rh].[Rh].[Rh];
Properties
Chemical formula	C16O16Rh6
Molar mass	1065.62 g/mol
Appearance	purple-brown solid
Melting point	235 °C (455 °F; 508 K)
Hazards
GHS pictograms
GHS Signal word	Warning
GHS hazard statements	H302, H312, H332
GHS precautionary statements	P261, P264, P270, P271, P280, P301+312, P302+352, P304+312, P304+340, P312, P322, P330, P363, P501
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

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.

Discovery and synthesis

Rh₆(CO)₁₆ was first prepared by Heiber in 1943 by carbonylation of RhCl₃·3H₂O at 80-230 °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

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

References

James, B. R.; Rempel, G. L.; Teo, W. K. (1976). Hexadecacarbonylhexarhodium. Inorg. Synth. Inorganic Syntheses. 16. p. 49. doi:10.1002/9780470132470.ch15. ISBN 9780470132470.
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.
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.
Booth, B. L.; Else, M. J.; Fields, R.; Goldwhite, H.; Haszeldine, R. N. (1968). "Metal carbonyl chemistry IV. The preparation of cobalt and rhodium carbonyls by reductive carbonylation with pentacarbonyliron". J. Organomet. Chem. 14 (2): 417–422. doi:10.1016/S0022-328X(00)87682-2.

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[IS-1] James, B. R.; Rempel, G. L.; Teo, W. K. (1976). Hexadecacarbonylhexarhodium. Inorg. Synth. Inorganic Syntheses. 16. p. 49. doi:10.1002/9780470132470.ch15. ISBN 9780470132470.

[2] 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.

[3] 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.

[encyc-4] Booth, B. L.; Else, M. J.; Fields, R.; Goldwhite, H.; Haszeldine, R. N. (1968). "Metal carbonyl chemistry IV. The preparation of cobalt and rhodium carbonyls by reductive carbonylation with pentacarbonyliron". J. Organomet. Chem. 14 (2): 417–422. doi:10.1016/S0022-328X(00)87682-2.