Rhodium(II) acetate

Rhodium(II) acetate
Names
IUPAC name
Rhodium(II) acetate
Other names
Dirhodium tetraacetate,
Tetrakis(acetato)dirhodium(II),
Rhodium diacetate dimer,
Tetrakis(μ-acetato)dirhodium
Identifiers
CAS Number
  • 15956-28-2 checkY
3D model (JSmol)
  • Interactive image
ChemSpider
  • 20370 checkY
ECHA InfoCard 100.036.425 Edit this at Wikidata
EC Number
  • 240-084-8
PubChem CID
  • 152122
RTECS number
  • VI9361000
UNII
  • NK3058Z56X checkY
CompTox Dashboard (EPA)
  • DTXSID201314246 Edit this at Wikidata
InChI
  • InChI=1S/2C2H4O2.Rh/c2*1-2(3)4;/h2*1H3,(H,3,4);/q;;+2/p-2 checkY
    Key: ITDJKCJYYAQMRO-UHFFFAOYSA-L checkY
  • InChI=1S/4C2H4O2.2Rh/c4*1-2(3)4;;/h4*1H3,(H,3,4);;/q;;;;2*+2/p-4
    Key: : SYBXSZMNKDOUCA-UHFFFAOYSA-J
  • [OH2][Rh+3]1234#[Rh+3]([OH2])(O[C-](C)O1)(O[C-](C)O2)(O[C-](C)O3)O[C-](C)O4
Properties
Chemical formula
C8H12O8Rh2
Molar mass 441.99 g/mol
Appearance Emerald green powder
Density 1.126 g/cm3
Melting point >100 °C
Boiling point decomposes
Solubility in water
soluble
Solubility in other solvents polar organic solvents
Structure
Crystal structure
monoclinic
Coordination geometry
octahedral
0 D
Hazards
GHS labelling:[1]
GHS07: Exclamation mark
Warning
H315, H319
P264, P280, P302+P352, P305+P351+P338, P321, P332+P313, P337+P313, P362
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point low flammability
Safety data sheet (SDS) Coleparmer MSDS
Related compounds
Related compounds
Copper(II) acetate
Chromium(II) acetate
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
Chemical compound

Rhodium(II) acetate is the coordination compound with the formula Rh2(AcO)4, where AcO is the acetate ion (CH
3
CO
2
). This dark green powder is slightly soluble in polar solvents, including water. It is used as a catalyst for cyclopropanation of alkenes. It is a widely studied example of a transition metal carboxylate complex.[2]

Preparation

Rhodium(II) acetate is usually prepared by the heating of hydrated rhodium(III) chloride in a methanol-acetic acid mixture. The crude product is the bis(methanol) complex, but it is easily desolvated.[2][3]

Structure and properties

The structure of rhodium(II) acetate features a pair of rhodium atoms, each with octahedral molecular geometry, defined by four acetate oxygen atoms, water, and a Rh–Rh bond of length 2.39 Å. The water adduct is exchangeable, and a variety of other Lewis bases bind to the axial positions.[4] Copper(II) acetate and chromium(II) acetate adopt similar structures.

Chemical properties

The dimer binds a number of classical Lewis bases to form 2:1 adducts:

Its Lewis acidity is eclipsed by the enhanced reactivity of rhodium(II) trifluoroacetate, which even binds arenes and alkenes.

The acetate group can be replaced by other carboxylates of strong acids. The yields are nearly quantitative.

Like almost all rhodium complexes, rhodium(II) acetate catalyzes many reactions such as hydrogenation and hydrosilylation. No evidence exists for mechanisms and the behavior has not motivated further work. The important observation that rhodium(II) acetate catalyzes reactions of diazo compounds has led to considerable research, but mostly focused on the trifluoroacetate or chiral derivatives.

References

  1. ^ "Dirhodium tetraacetate". pubchem.ncbi.nlm.nih.gov. Retrieved 14 December 2021.
  2. ^ a b Felthouse, Timothy R. (1982). "The Chemistry, Structure, and Metal-Metal Bonding in Compounds of Rhodium(II)". Progress in Inorganic Chemistry. Vol. 29. pp. 73–166. doi:10.1002/9780470166307.ch2. ISBN 978-0-471-09370-1.
  3. ^ Rempel, G. A.; Legzdins, P.; Smith, H.; Wilkinson, G. (1972). "Tetrakis(acetato)dirhodium(II) and Similar Carboxylato Compounds". Inorganic Syntheses. Vol. 13. pp. 90–91. doi:10.1002/9780470132449.ch16. ISBN 9780470132449. {{cite book}}: |journal= ignored (help)
  4. ^ Cotton, F. A.; Deboer, B. G.; Laprade, M. D.; Pipal, J. R.; Ucko, D. A. (1971). "The crystal and molecular structures of dichromium tetraacetate dihydrate and dirhodium tetraacetate dihydrate". Acta Crystallogr B. 27 (8): 1664. doi:10.1107/S0567740871004527.
  • v
  • t
  • e
Rh(0)
Organorhodium(0) compounds
  • Rh4(CO)12
  • Rh6(CO)16
Rh(I)
  • RhCl(P(C6H5)3)3
Organorhodium(I) compounds
  • ((C2H4)2RhCl)2
  • ((C8H12)RhCl)2
  • ((C8H14)2RhCl)2
  • ((CO)2RhCl)2
  • HRh(P(C6H5)3)4
  • HRh(CO)(P(C6H5)3)3
Rh(II)
  • Rh2(CH3CO2)4
Organorhodium(II) compunds
  • Rh(C5H5)2
Rh(III)
  • RhBr3
  • Rh(C5H5N)4Cl3
  • RhCl3
  • Rh(ClO4)3
  • RhF3
  • Rh(OH)3
  • RhI3
  • Rh(NH3)5ClCl2
  • Rh(NO3)3
  • Rh2O3
  • Rh2S3
  • Rh2(SO4)3
  • YbRh2Si2
Organorhodium(III) compunds
  • ((CH3)5C5RhCl2)2
  • Rh(O2C5H7)3
  • Rh(IV)
    • RhO2
    • RhF4
    Rh(V)
    • RhF5
    • XeRhF6
    Rh(VI)
    • RhF6
    • v
    • t
    • e
    Acetyl halides and salts of the acetate ion
    AcOH He
    LiOAc Be(OAc)2
    Be4O(OAc)6
    B(OAc)3
    B2O(OAc)4
    AcOAc
    ROAc
    NH4OAc AcOOH FAc
    FOAc
    Ne
    NaOAc
    NaH(OAc)2
    Mg(OAc)2 Al(OAc)3
    ALSOL
    Al(OAc)2OH
    Al(OH)2OAc
    Al2SO4(OAc)4
    Si P S ClAc
    ClOAc
    Ar
    KOAc Ca(OAc)2 Sc(OAc)3 Ti(OAc)4 VO(OAc)3 Cr(OAc)2
    Cr(OAc)3
    Mn(OAc)2
    Mn(OAc)3
    Fe(OAc)2
    Fe(OAc)3
    Co(OAc)2 Ni(OAc)2 CuOAc
    Cu(OAc)2
    Zn(OAc)2 Ga(OAc)3 Ge As(OAc)3 Se BrAc
    BrOAc
    Kr
    RbOAc Sr(OAc)2 Y(OAc)3 Zr(OAc)4 Nb Mo(OAc)2 Tc Ru2(OAc)4Cl
    Ru(OAc)3
    Rh2(OAc)4 Pd(OAc)2 AgOAc Cd(OAc)2 In(OAc)3 Sn(OAc)2
    Sn(OAc)4
    Sb(OAc)3 Te IAc
    IOAc
    I(OAc)3
    Xe
    CsOAc Ba(OAc)2 * Lu(OAc)3 Hf Ta W Re Os Ir Pt(OAc)2 Au(OAc)3 Hg2(OAc)2
    Hg(OAc)2
    TlOAc
    Tl(OAc)3
    Pb(OAc)2
    Pb(OAc)4
    Bi(OAc)3 Po At Rn
    Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
     
    * La(OAc)3 Ce(OAc)3 Pr(OAc)3 Nd(OAc)3 Pm Sm(OAc)3 Eu(OAc)3 Gd(OAc)3 Tb(OAc)3 Dy(OAc)3 Ho(OAc)3 Er(OAc)3 Tm(OAc)3 Yb(OAc)3
    ** Ac(OAc)3 Th(OAc)4 Pa UO2(OAc)2 Np Pu Am Cm Bk Cf Es Fm Md No