Redox-active nickel and cobalt tris(pyrazolyl)borate dithiocarbamate complexes: air-stable Co(ii) dithiocarbamatesCCDC reference numbers 789217–789219. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c0dt01010c.
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| Title: | Redox-active nickel and cobalt tris(pyrazolyl)borate dithiocarbamate complexes: air-stable Co(ii) dithiocarbamatesCCDC reference numbers 789217–789219. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c0dt01010c. |
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| Authors: | David J. Harding1, Phimphaka Harding1, Supaporn Dokmaisrijan1, Harry Adams2 |
| Source: | Dalton Transactions: An International Journal of Inorganic Chemistry. Jan2011, Vol. 40 Issue 6, p1313-1321. 9p. |
| Subjects: | Oxidation-reduction reaction, Dithiocarbamates, Nickel, Cobalt, Crystallography, Infrared spectroscopy, Chemical reactions |
| Abstract: | A series of new cobalt(ii) and nickel(ii) tris(3,5-diphenylpyrazolyl)borate (TpPh2) dithiocarbamate complexes [TpPh2M(dtc)] (M = Co, dtc = S2CNEt21, S2CNBz22and S2CN(CH2)43; M = Ni, dtc = S2CNEt24, S2CNBz25and S2CN(CH2)46) have been prepared by the reaction of [TpPh2MBr] with Nadtc in CH2Cl2. IR spectroscopy indicates that the TpPh2ligand is κ3coordinated while the dithiocarbamate ligand is κ2coordinated. 1H NMR and UV-Vis spectroscopy are consistent with high spin, five-coordinate metal centres. X-ray crystallographic studies of 1, 3and 6confirm the κ3coordination of the TpPh2ligand and reveal an intermediate five-coordinate geometry with an asymmetrically coordinated dithiocarbamate ligand. Electrochemical studies of 1–6reveal a metal centred reversibleone-electron oxidation to M(iii). Attempted oxidation of [TpPh2Co(dtc)] with [FeCpCpCOMe]BF4yields [Co(dtc)3], HpzPh2and a further product which may be [TpPh2CoBpPh2]. DFT calculations indicate that the low redox potentials in these complexes result from a strongly antibonding M–S σ* HOMO. [ABSTRACT FROM AUTHOR] |
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| Database: | Engineering Source |
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