View : 476 Download: 0
Deeper Understanding of Mononuclear Manganese(IV)-Oxo Binding Bronsted and Lewis Acids and the Manganese(IV)-Hydroxide Complex
- Title
- Deeper Understanding of Mononuclear Manganese(IV)-Oxo Binding Bronsted and Lewis Acids and the Manganese(IV)-Hydroxide Complex
- Authors
- Karmalkar, Deepika G.; Seo, Mi Sook; Lee, Yong-Min; Kim, Youngsuk; Lee, Eunsung; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민; 서미숙
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민; 서미숙
- Issue Date
- 2021
- Journal Title
- INORGANIC CHEMISTRY
- ISSN
- 0020-1669
1520-510X
- Citation
- INORGANIC CHEMISTRY vol. 60, no. 22, pp. 16996 - 17007
- Publisher
- AMER CHEMICAL SOC
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Binding of Lewis acidic metal ions and Bronsted 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)Mn-IV(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., nu(Mn-O) at similar to 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)Mn-IV(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)Mn-IV(OH)](OTf)(2) (4), with a Mn-O bond distance of 1.8043(19) angstrom 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.
- 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