Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Tak, Hyeonwoo | - |
dc.contributor.author | Lee, Hyunjoo | - |
dc.contributor.author | Kang, Joongoo | - |
dc.contributor.author | Cho, Jaeheung | - |
dc.date.available | 2017-07-11T04:40:30Z | - |
dc.date.created | 2017-04-10 | - |
dc.date.issued | 2016 | - |
dc.identifier.issn | 2052-1553 | - |
dc.identifier.uri | http://hdl.handle.net/20.500.11750/2569 | - |
dc.description.abstract | A nickel(ii)-borohydride complex bearing a macrocyclic tridentate N-donor ligand, [Ni(Me3-TACN)(BH4)(CH3CN)]+ (Me3-TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane), was prepared, isolated, and characterized by various physicochemical methods, including UV-vis, ESI-MS, IR and X-ray analyses. The structural and spectroscopic characterization clearly shows that the borohydride ligand is bound to the high-spin nickel(ii) center in an η2-manner. Density functional theory calculations provided geometric information of 2, showing that the η2-binding of borohydride to the nickel center is more favorable than the η3-binding mode in CH3CN. The complex is paramagnetic with an effective magnetic moment of 2.9μB consistent with a d8 high-spin system. The reactivity of the high-spin nickel(ii)-borohydride complex was examined in dehalogenation with numerous halocarbons. A kinetic isotope effect value of 1.7 was observed in the dehalogenation of CHCl3 by the nickel(ii)-borohydride complex. Kinetic studies and isotopic labeling experiments implicate that hydride ion or hydrogen atom transfer from the borohydride group is the rate determining step. The positive Hammett ρ value of 1.2, obtained in the reactions of [Ni(Me3-TACN)(BH4)(CH3CN)]+ and para-substituted benzoyl chloride, indicates that the dehalogenation by the nickel(ii)-borohydride species occurs via a nucleophilic reaction. © the Partner Organisations 2016. | - |
dc.language | English | - |
dc.publisher | Royal Society of Chemistry | - |
dc.title | A high-spin nickel(II) borohydride complex in dehalogenation | - |
dc.type | Article | - |
dc.identifier.doi | 10.1039/c5qi00206k | - |
dc.identifier.scopusid | 2-s2.0-84954209100 | - |
dc.identifier.bibliographicCitation | Inorganic Chemistry Frontiers, v.3, no.1, pp.157 - 163 | - |
dc.description.isOpenAccess | FALSE | - |
dc.subject.keywordPlus | 1,2-DICHLOROETHANE | - |
dc.subject.keywordPlus | CARBON-DIOXIDE | - |
dc.subject.keywordPlus | COENZYME-M | - |
dc.subject.keywordPlus | METAL | - |
dc.subject.keywordPlus | METHANOBACTERIUM | - |
dc.subject.keywordPlus | REDUCTIVE DECHLORINATION | - |
dc.subject.keywordPlus | Resonance | - |
dc.citation.endPage | 163 | - |
dc.citation.number | 1 | - |
dc.citation.startPage | 157 | - |
dc.citation.title | Inorganic Chemistry Frontiers | - |
dc.citation.volume | 3 | - |
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