Rhodium(II) trifluoroacetate

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Rhodium(II) trifluoroacetate
File:Rh2(tfa)4(H2O)2.svg
Names
Other names
  • Dirhodium tetrakis(trifluoroacetate)
  • Dirhodium tetra(trifluoroacetate)
  • Rhodium(II) trifluoroacetate dimer
Identifiers
3D model (JSmol)
ChemSpider
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EC Number
  • 631-136-4
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  • InChI=1S/4C2HF3O2.2Rh/c4*3-2(4,5)1(6)7;;/h4*(H,6,7);;
    Key: SZQVMUPTZFMHQT-UHFFFAOYSA-N
  • C(=O)(C(F)(F)F)O.C(=O)(C(F)(F)F)O.C(=O)(C(F)(F)F)O.C(=O)(C(F)(F)F)O.[Rh].[Rh]
Properties
C8F12O8Rh2
Molar mass 657.872 g·mol−1
Appearance green solid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Rhodium trifluoroacetate is the chemical compound with the formula Rh2(O2CCF3)4. It is used as a catalyst in the synthesis of some organic compounds.[1] The compound and its derivatives have been extensively characterized by X-ray crystallography. It adopts the Chinese lantern structure seen for many dimetal carboxylate complexes. This structure accommodates a Rh-Rh bond, the existence of which explains the diamagnetism of this Rh(II) species. The Rh-Rh distance is 238 pm.[2]

The anhydrous complex is a green volatile solid. It is prepared by dissolving rhodium(II) acetate in hot trifluoroacetic acid:[3]

Rh2(O2CCH3)4 + 4 HO2CCF3 → Rh2(O2CCF3)4 + 4 HO2CCH3

This reaction expels acetic acid. The Rh-Rh bond is retained.

Reactions

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Rhodium(II) trifluoroacetate forms adducts with a variety of Lewis bases. The structures typically have a 2:1 stoichiometry, with one base binding at the "axial" position on each of the two Rh(II) centers:

Rh2(O2CCF3)4 + 2 L → Rh2(O2CCF3)4L2 (L = CO, RCN, R2SO, R3P, ...)

Rhodium(II) trifluoroacetate binds even very weak bases, moreso than does rhodium(II) acetate. It even forms adducts with hexamethylbenzene and with S8.[4]

Rhodium(II) trifluoroacetate catalyzes cyclopropanation of alkenes by diazo compounds:[1] RCH=CR'H + CH3CH2O2CCH(N2) → cyclo−(RCH)(R'CH)(CH3CH2O2CCH) + N2

References

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