Cobalt tris(diethyldithiocarbamate)

Cobalt tris(diethyldithiocarbamate)

Names
IUPAC name Tris(diethyldithiocarbamato)cobalt
Other names Cobalt diethyl dithiocarbamate; cobalt(3+);N,N-diethylcarbamodithioate
Identifiers
CAS Number	13963-60-5
3D model (JSmol)	Interactive image
ChemSpider	67160271
PubChem CID	13981569
InChI InChI=1S/3C5H11NS2.Co/c3*1-3-6(4-2)5(7)8;/h3*3-4H2,1-2H3,(H,7,8);/q;;;+3/p-3 Key: JBNCRGZHNOJKHG-UHFFFAOYSA-K
SMILES CCN(CC)C(=S)[S-].CCN(CC)C(=S)[S-].CCN(CC)C(=S)[S-].[Co+3]
Properties
Chemical formula	[(C2H5)2NCS2]3Co
Molar mass	416.5 g/mol
Appearance	green solid
Density	1.43 g/cm^3
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

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]

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

• Iron tris(diethyldithiocarbamate) - a related dimethyldithiocarbamate complex of iron

References

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. 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. 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. 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.