Highly Reactive Manganese(IV)-Oxo Porphyrins Showing Temperature-Dependent Reversed Electronic Effect in C-H Bond Activation Reactions

Mian Guo, Mi Sook Seo, Yong Min Lee, Shunichi Fukuzumi, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

47 Scopus citations

Abstract

We report that Mn(IV)-oxo porphyrin complexes, MnIV(O)(TMP) (1) and MnIV(O)(TDCPP) (2), are capable of activating the C-H bonds of hydrocarbons, including unactivated alkanes such as cyclohexane, via an oxygen non-rebound mechanism. Interestingly, 1 with an electron-rich porphyrin is more reactive than 2 with an electron-deficient porphyrin at a high temperature (e.g., 0 °C). However, at a low temperature (e.g., -40 °C), the reactivity of 1 and 2 is reversed, showing that 2 is more reactive than 1. To the best of our knowledge, the present study reports the first example of highly reactive Mn(IV)-oxo porphyrins and their temperature-dependent reactivity in C-H bond activation reactions.

Original languageEnglish
Pages (from-to)12187-12191
Number of pages5
JournalJournal of the American Chemical Society
Volume141
Issue number31
DOIs
StatePublished - 7 Aug 2019

Bibliographical note

Funding Information:
This work was supported by the NRF of Korea through CRI (NRF-2012R1A3A2048842 to W.N.), GRL (NRF-2010-00353 to W.N.) and Basic Science Research Program (2017R1D1A1B03029982 to Y.-M.L. and 2017R1D1A1B03032615 to S.F.), and Grants-in-Aid (no. 16H02268 to S.F.) from JSPS (MEXT), Japan. W.N. acknowledges the use of resonance Raman facility at IBS (IBS-R10-A1) in Korea.

Publisher Copyright:
© 2019 American Chemical Society.

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