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Hexadecacarbonylhexarhodium

From Wikipedia, the free encyclopedia
Hexadecacarbonylhexarhodium
Names
IUPAC name
Hexadecacarbonylhexarhodium
Other names
Hexarhodium hexadecacarbonyl
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard100.044.539Edit this at Wikidata
EC Number
  • 249-009-3
  • InChI=1S/16CO.6Rh/c16*1-2;;;;;;
    Key: SZQABOJVTZVBHE-UHFFFAOYSA-N
  • [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
C16O16Rh6
Molar mass1065.62 g/mol
Appearancepurple-brown solid
Melting point235 °C (455 °F; 508 K)
Hazards
GHS labelling:
GHS07: Exclamation mark
Warning
H302,H312,H332
P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P312,P304+P340,P312,P322,P330,P363,P501
Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa).
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Chemical compound

Hexadecacarbonylhexarhodium is ametal 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

[edit]

Rh6(CO)16 was first prepared byWalter Hieber in 1943 by carbonylation ofRhCl3·3H2O at 80–230 °C and 200 atmcarbon 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. usingX-ray crystallography. The correct CO/Rh ratio is 2.66.[3]

Relative to the original preparation, the carbonylation of a mixture of anhydrousrhodium trichloride andiron 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 andrhodium(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 oftetrarhodium dodecacarbonyl in boiling hexane:[5]

3 Rh4(CO)12 → 2 Rh6(CO)16 + 4 CO

Reactions

[edit]

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

Rh6(CO)16 catalyzes a number of organic reactions includinghydrogenation andhydroformylation.[4]

References

[edit]
  1. ^abJames, B. R.; Rempel, G. L.; Teo, W. K. (1976). "Hexadecacarbonylhexarhodium".Inorg. Synth.16: 49.doi:10.1002/9780470132470.ch15.
  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.
  4. ^abBooth, 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.
  5. ^abTunik, S. P.; Vlasov, A. V.; Krivykh, V. V. (1977). "Acetonitrile-Substituted Derivatives of Rh6(CO)16 : Rh6(CO)16-x(NCMe)x (x = 1,2)".Inorganic Syntheses.31:239–244.doi:10.1002/9780470132623.ch37.
Rh(0)
Organorhodium(0) compounds
Rh(I)
Organorhodium(I) compounds
Rh(II)
Organorhodium(II) compunds
Rh(III)
Organorhodium(III) compunds
Rh(IV)
Rh(V)
Rh(VI)
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