Cobalt tris(diethyldithiocarbamate) explained
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. Cobalt tris(diethyldithiocarbamate) is an octahedral coordination complex of low-spin Co(III) with idealized D3 symmetry. The Co-S distances are 267 pm.[2]
Reactions
Oxidation of Co(Et2dtc)3 occurs at mild potentials to give the cobalt(IV) derivative.[3]
Treatment of Co(Et2dtc)3 with fluoroboric acid results in the removal of 0.5 equiv of ligand giving a binuclear cation:[4]
2Co(Et2dtc)3 + HBF4 → [Co<sub>2</sub>(Et<sub>2</sub>dtc)<sub>5</sub>]BF4 + "Et2NdtcH"
See also
Notes and References
- The Chemistry of the Dithioacid and 1,1-Dithiolate Complexes. Progress in Inorganic Chemistry. 11. D. Coucouvanis. 2007. 233–371. 10.1002/9780470166123.ch4. 9780470166123.
- 10.1071/CH9901083. Alkyl Substituent Effects in Diamagnetic Dithiocarbamate Cobalt(III) and Nickel(II) Complexes. 1990. Healy. PC. Connor. J. W.. Skelton. B. W.. White. A. H.. Australian Journal of Chemistry. 43. 6. 1083.
- 10.1039/b104636p. Voltammetric, EPR and UV-VIS-NIR spectroscopic studies Associated with the Characterisation of Electrochemically Generated Tris(dithiocarbamato)cobalt(IV) Complexes in Dichloromethane . 2001 . Webster . Richard D. . Heath . Graham A. . Bond . Alan M.. Journal of the Chemical Society, Dalton Transactions . 21 . 3189–3195 .
- 10.1039/dt9750002182. Synthesis and Properties of Dimeric Cobalt(III) Dithiocarbamate Complexes [Co2(R2dtc)5]+: X-Ray Structural Analysis of Pentakis(diethyldithiocarbamato)dicobalt(III) Tetrafluoroborate. 1975. Hendrickson. Alan R.. Martin. Raymond L.. Taylor. Donald. Journal of the Chemical Society, Dalton Transactions. 21. 2182.
