View : 17 Download: 0

Enhanced electron-transfer reactivity of nonheme manganese(IV)-oxo complexes by binding scandium ions

Title
Enhanced electron-transfer reactivity of nonheme manganese(IV)-oxo complexes by binding scandium ions
Authors
Yoon H.Lee Y.-M.Wu X.Cho K.-B.Sarangi R.Nam W.Fuhkuzumi S.
Ewha Authors
남원우Shunichi Fukuzumi이용민
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 이용민scopusscopus
Issue Date
2013
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 135, no. 24, pp. 9186 - 9194
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
One and two scandium ions (Sc3+) are bound strongly to nonheme manganese(IV)-oxo complexes, [(N4Py)MnIV(O)]2+ (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine) and [(Bn-TPEN)Mn IV(O)]2+ (Bn-TPEN = N-benzyl-N,N′,N′-tris(2- pyridylmethyl)-1,2-diaminoethane), to form MnIV(O)-(Sc 3+)1 and MnIV(O)-(Sc3+)2 complexes, respectively. The binding of Sc3+ ions to the Mn IV(O) complexes was examined by spectroscopic methods as well as by DFT calculations. The one-electron reduction potentials of the Mn IV(O) complexes were markedly shifted to a positive direction by binding of Sc3+ ions. Accordingly, rates of the electron transfer reactions of the MnIV(O) complexes were enhanced as much as 10 7-fold by binding of two Sc3+ ions. The driving force dependence of electron transfer from various electron donors to the Mn IV(O) and MnIV(O)-(Sc3+)2 complexes was examined and analyzed in light of the Marcus theory of electron transfer to determine the reorganization energies of electron transfer. The smaller reorganization energies and much more positive reduction potentials of the MnIV(O)-(Sc3+)2 complexes resulted in remarkable enhancement of the electron-transfer reactivity of the Mn IV(O) complexes. Such a dramatic enhancement of the electron-transfer reactivity of the MnIV(O) complexes by binding of Sc3+ ions resulted in the change of mechanism in the sulfoxidation of thioanisoles by MnIV(O) complexes from a direct oxygen atom transfer pathway without metal ion binding to an electron-transfer pathway with binding of Sc 3+ ions. © 2013 American Chemical Society.
DOI
10.1021/ja403965h
Appears in Collections:
자연과학대학 > 화학·나노과학전공 > Journal papers
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML


qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE