期刊
INORGANIC CHEMISTRY
卷 61, 期 10, 页码 4292-4301出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.1c03104
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资金
- National Research Foundation of Korea (NRF) through the Ministry of Science, ICT, and Future Planning [2019R1A2C2086249, 2021R1A2C1012851]
- National Research Foundation of Korea [2019R1A2C2086249, 2021R1A2C1012851] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
This study reports the structure and spectroscopic characteristics of high-valent transition metal-hydroxide complexes and demonstrates their oxidative reactivity, highlighting their significance in catalytic reactions.
High-valent transition metal-hydroxide complexes havebeen proposed as essential intermediates in biological and syntheticcatalytic reactions. In this work, we report the single-crystal X-raystructure and spectroscopic characteristics of a mononuclear non-porphyrinic MnIV-(OH) complex, [MnIV(Me3-TPADP)(OH)-(OCH2CH3)]2+(2), using various physicochemical methods. Likewise,[MnIV(Me3-TPADP)(OH)(OCH2CF3)]2+(3), which is thermally stableat room temperature, was also synthesized and characterized spectroscopically. The MnIV-(OH) adducts are capable of performingoxidation reactions with external organic substrates such as C-H bond activation, sulfoxidation, and epoxidation. Kinetic studies,involving the Hammett correlation and kinetic isotope effect, and product analyses indicate that2and3exhibit electrophilicoxidative reactivity toward hydrocarbons. Density functional theory calculations support the assigned electronic structure and showthat direct C-H bond activation of the MnIV-(OH) species is indeed possible.
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