Sodium tris(carbonato)cobalt(III)

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Sodium tris(carbonato)cobalt(III)
Identifiers
3D model (
JSmol
)
ChemSpider
  • InChI=1S/3CH2O3.Co.3Na.3H2O/c3*2-1(3)4;;;;;;;/h3*(H2,2,3,4);;;;;3*1H2/q;;;+3;3*+1;;;/p-6
    Key: RAXRATBBPMSPAF-UHFFFAOYSA-H
  • C(=O)([O-])[O-].C(=O)([O-])[O-].C(=O)([O-])[O-].[Na+].[Na+].[Na+].[Co+3].O.O.O
Properties
C3H6CoNa3O12
Molar mass 361.972 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).

Sodium tris(carbonato)cobalt(III) is the

metal carbonato complex, is sometimes referred to as the “Field-Durrant precursor” and is prepared by the “Field-Durrant synthesis”. It is used in the synthesis of other cobalt(III) complexes. Otherwise cobalt(III) complexes are generated from cobalt(II) precursors, a process that requires an oxidant.[1]

Synthesis

An aqueous solution of cobalt(II) nitrate and hydrogen peroxide is added to a solution of sodium bicarbonate, leading to precipitation of the olive solid.[2] The method is a modification of the synthesis of what has been described as “Co2(CO3)3”.[3]

Structure and synthetic applications

The identity of this complex anion is uncertain, suggestions include [Co(κ2-CO3)3]3-, [Co(κ1-CO3H)3(OH)3]3-, and [Co(κ2-CO3)2(κ1-CO3)(OH2)]3-. Thermal gravimetric analysis favors the presence of one aquo ligand,

infra-red spectroscopy indicates the presence of both bi- and unidentate carbonate ligands. The addition of [Co(NH3)6]Cl3 to fresh solutions of sodium tris(carbonato)cobalt(III) precipitates anhydrous salt [Co(NH3)6] [Co(κ2-CO3)3]. This salt has been characterized by X-ray crystallography, which established that the anionic complex features three bidentate (κ2-) carbonate ligands.[5]

To some extent, the exact description of the title salt is unimportant since it is only used as a synthetic intermediate, it has no intrinsic value. Products include [Co(H2O)6]3+, [Co(κ2-CO3)(H2O)4]+, and [Co(κ2-CO3)2(H2O)2]− and their derivatives where the

aquo ligand has been displaced.[5] The closely related potassium tris(carbonatocobalt(III) has also been used for the preparation of diverse complexes. These derivatives include [Co(NH3)2(κ2-CO3)2]− and [Co(CN)2(κ2-CO3)2]3-, rare examples of biscarbonato cobalt(III) complexes. Other derivatives include the dinitrite [Co(NH3)2(κ2-CO3)(NO2)2]− and the oxalate [Co(NH3)2(κ2-CO3)(C2O4)]−.[6]

Other literature

References

  1. doi:10.1021/cr60264a001
    .
  2. ISBN 9780470132395
    .
  3. ^ Duval, C. (1930). "Sur le Cobalticarbonate Cobaltique". Rendus Hebdomadaires des Séances de l'Académie des Sciences. 191.
  4. S2CID 97142236
    .
  5. ^
    doi:10.1016/S0020-1693(02)01236-7
    .
  6. ISBN 978-0-471-81873-1
    .
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