skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

Abstract

Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N 5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc 3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

Authors:
; ; ; ; ; ; ; ; ; ;  [1]
  1. Ewha
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
FOREIGN
OSTI Identifier:
1081345
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 135; Journal Issue: (17) ; 05, 2013; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Chen, Junying, Lee, Yong-Min, Davis, Katherine M., Wu, Xiujuan, Seo, Mi Sook, Cho, Kyung-Bin, Yoon, Heejung, Park, Young Jun, Fukuzumi, Shunichi, Pushkar, Yulia N., Nam, Wonwoo, Purdue), and Osaka). A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions. United States: N. p., 2013. Web. doi:10.1021/ja312113p.
Chen, Junying, Lee, Yong-Min, Davis, Katherine M., Wu, Xiujuan, Seo, Mi Sook, Cho, Kyung-Bin, Yoon, Heejung, Park, Young Jun, Fukuzumi, Shunichi, Pushkar, Yulia N., Nam, Wonwoo, Purdue), & Osaka). A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions. United States. doi:10.1021/ja312113p.
Chen, Junying, Lee, Yong-Min, Davis, Katherine M., Wu, Xiujuan, Seo, Mi Sook, Cho, Kyung-Bin, Yoon, Heejung, Park, Young Jun, Fukuzumi, Shunichi, Pushkar, Yulia N., Nam, Wonwoo, Purdue), and Osaka). Wed . "A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions". United States. doi:10.1021/ja312113p.
@article{osti_1081345,
title = {A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions},
author = {Chen, Junying and Lee, Yong-Min and Davis, Katherine M. and Wu, Xiujuan and Seo, Mi Sook and Cho, Kyung-Bin and Yoon, Heejung and Park, Young Jun and Fukuzumi, Shunichi and Pushkar, Yulia N. and Nam, Wonwoo and Purdue) and Osaka)},
abstractNote = {Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.},
doi = {10.1021/ja312113p},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = (17) ; 05, 2013,
volume = 135,
place = {United States},
year = {2013},
month = {5}
}