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] |
| Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
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| Items | – Name: Title Label: Title Group: Ti Data: 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. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22David+J%2E+Harding%22">David J. Harding</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Phimphaka+Harding%22">Phimphaka Harding</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Supaporn+Dokmaisrijan%22">Supaporn Dokmaisrijan</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Harry+Adams%22">Harry Adams</searchLink><relatesTo>2</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. Jan2011, Vol. 40 Issue 6, p1313-1321. 9p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Oxidation-reduction+reaction%22">Oxidation-reduction reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Dithiocarbamates%22">Dithiocarbamates</searchLink><br /><searchLink fieldCode="DE" term="%22Nickel%22">Nickel</searchLink><br /><searchLink fieldCode="DE" term="%22Cobalt%22">Cobalt</searchLink><br /><searchLink fieldCode="DE" term="%22Crystallography%22">Crystallography</searchLink><br /><searchLink fieldCode="DE" term="%22Infrared+spectroscopy%22">Infrared spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/c0dt01010c Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 9 StartPage: 1313 Subjects: – SubjectFull: Oxidation-reduction reaction Type: general – SubjectFull: Dithiocarbamates Type: general – SubjectFull: Nickel Type: general – SubjectFull: Cobalt Type: general – SubjectFull: Crystallography Type: general – SubjectFull: Infrared spectroscopy Type: general – SubjectFull: Chemical reactions Type: general Titles: – TitleFull: 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. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: David J. Harding – PersonEntity: Name: NameFull: Phimphaka Harding – PersonEntity: Name: NameFull: Supaporn Dokmaisrijan – PersonEntity: Name: NameFull: Harry Adams IsPartOfRelationships: – BibEntity: Dates: – D: 25 M: 01 Text: Jan2011 Type: published Y: 2011 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 40 – Type: issue Value: 6 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
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