View : 14 Download: 0

Deeper Understanding of Mononuclear Manganese(IV)-Oxo Binding Brønsted and Lewis Acids and the Manganese(IV)-Hydroxide Complex

Title
Deeper Understanding of Mononuclear Manganese(IV)-Oxo Binding Brønsted and Lewis Acids and the Manganese(IV)-Hydroxide Complex
Authors
Karmalkar D.G.Seo M.S.Lee Y.-M.Kim Y.Lee E.Sarangi R.Fukuzumi S.Nam W.
Ewha Authors
남원우Shunichi Fukuzumi이용민서미숙
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopusscopus; 이용민scopusscopusscopus; 서미숙scopus
Issue Date
2021
Journal Title
Inorganic Chemistry
ISSN
0020-1669JCR Link
Citation
Inorganic Chemistry vol. 60, no. 22, pp. 16996 - 17007
Publisher
American Chemical Society
Indexed
SCIE; SCOPUS scopus
Document Type
Article
Abstract
Binding of Lewis acidic metal ions and Brønsted acid at the metal-oxo group of high-valent metal-oxo complexes enhances their reactivities significantly in oxidation reactions. However, such a binding of Lewis acids and proton at the metal-oxo group has been questioned in several cases and remains to be clarified. Herein, we report the synthesis, characterization, and reactivity studies of a mononuclear manganese(IV)-oxo complex binding triflic acid, {[(dpaq)MnIV(O)]-HOTf}+ (1-HOTf). First, 1-HOTf was synthesized and characterized using various spectroscopic techniques, including resonance Raman (rRaman) and X-ray absorption spectroscopy/extended X-ray absorption fine structure. In particular, in rRaman experiments, we observed a linear correlation between the Mn-O stretching frequencies of 1-HOTf (e.g., νMn-O at â 793 cm-1) and 1-Mn+ (Mn+ = Ca2+, Zn2+, Lu3+, Al3+, or Sc3+) and the Lewis acidities of H+ and Mn+ ions, suggesting that H+ and Mn+ bind at the metal-oxo moiety of [(dpaq)MnIV(O)]+. Interestingly, a single-crystal structure of 1-HOTf was obtained by X-ray diffraction analysis, but the structure was not an expected Mn(IV)-oxo complex but a Mn(IV)-hydroxide complex, [(dpaq)MnIV(OH)](OTf)2 (4), with a Mn-O bond distance of 1.8043(19) Å and a Mn-O stretch at 660 cm-1. More interestingly, 4 reverted to 1-HOTf upon dissolution, demonstrating that 1-HOTf and 4 are interconvertible depending on the physical states, such as 1-HOTf in solution and 4 in isolated solid. The reactivity of 1-HOTf was investigated in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions and then compared with those of 1-Mn+ complexes; an interesting correlation between the Mn-O stretching frequencies of 1-HOTf and 1-Mn+ and their reactivities in the OAT and HAT reactions is reported for the first time in this study. © 2021 American Chemical Society.
DOI
10.1021/acs.inorgchem.1c02119
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