Cobalt_tris(diethyldithiocarbamate)

Cobalt tris(diethyldithiocarbamate)

Cobalt tris(diethyldithiocarbamate)

Chemical compound

Cobalt tris(diethyldithiocarbamate) is the coordination complex of cobalt with diethyldithiocarbamate with the formula Co(S2CNEt2)3 (Et = ethyl). It is a diamagnetic green solid that is soluble in organic solvents.[1]

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Synthesis, structure, bonding

Cobalt tris(dithiocarbamate)s are typically are prepared by air-oxidation of mixtures of dithiocarbamate salts and a cobalt(II) nitrate.[2] Cobalt tris(diethyldithiocarbamate) is an octahedral coordination complex of low-spin Co(III) with idealized D3 symmetry. The Co-S distances are 267 pm.[3]

Reactions

Oxidation of Co(Et2dtc)3 occurs at mild potentials to give the cobalt(IV) derivative.[2]

Treatment of Co(Et2dtc)3 with fluoroboric acid results in the removal of 0.5 equiv of ligand giving a binuclear cation:[4]

2 Co(Et2dtc)3 + HBF4 → [Co2(Et2dtc)5]BF4 + "Et2NdtcH"

See also

References

  1. [1]
    D. Coucouvanis (2007). "The Chemistry of the Dithioacid and 1,1-Dithiolate Complexes". Progress in Inorganic Chemistry. 11: 233–371. doi:10.1002/9780470166123.ch4. ISBN 9780470166123.
  2. [2]
    Webster, Richard D.; Heath, Graham A.; Bond, Alan M. (2001). "Voltammetric, EPR and UV-VIS-NIR spectroscopic studies Associated with the Characterisation of Electrochemically Generated Tris(dithiocarbamato)cobalt(IV) Complexes in Dichloromethane". Journal of the Chemical Society, Dalton Transactions (21): 3189–3195. doi:10.1039/b104636p.
  3. [3]
    Healy, PC; Connor, J. W.; Skelton, B. W.; White, A. H. (1990). "Alkyl Substituent Effects in Diamagnetic Dithiocarbamate Cobalt(III) and Nickel(II) Complexes". Australian Journal of Chemistry. 43 (6): 1083. doi:10.1071/CH9901083.
  4. [4]
    Hendrickson, Alan R.; Martin, Raymond L.; Taylor, Donald (1975). "Synthesis and Properties of Dimeric Cobalt(III) Dithiocarbamate Complexes [Co2(R2dtc)5]+: X-Ray Structural Analysis of Pentakis(diethyldithiocarbamato)dicobalt(III) Tetrafluoroborate". Journal of the Chemical Society, Dalton Transactions (21): 2182. doi:10.1039/dt9750002182.
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