A Mononuclear Non-Heme Manganese(IV)鈥揙xo Complex Binding Redox-Inactive Metal Ions

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• 作者：Junying Chen ; Yong-Min Lee ; Katherine M. Davis ; Xiujuan Wu ; Mi Sook Seo ; Kyung-Bin Cho ; Heejung Yoon ; Young Jun Park ; Shunichi Fukuzumi ; Yulia N. Pushkar ; Wonwoo Nam
• 刊名：The Journal of the American Chemical Society
• 出版年：2013
• 出版时间：May 1, 2013
• 年：2013
• 卷：135
• 期：17
• 页码：6388-6391
• 全文大小：314K
• 年卷期：v.135,no.17(May 1, 2013)
• ISSN：1520-5126

文摘

Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal鈥搊xo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)鈥搊xo complex bearing a pentadentate N₅ ligand has been synthesized and used in the synthesis of a Mn(IV)鈥搊xo complex binding scandium ions. The Mn(IV)鈥搊xo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)鈥搊xo 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鈥揌 bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)鈥搊xo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal鈥搊xo species in the oxygen atom transfer and hydrogen atom transfer reactions.