N2O Activation and Oxidation Reactivity from a Non-Heme Iron Pyrrole Platform

详细信息    查看全文

• 作者：W. Hill Harman ; Christopher J. Chang
• 刊名：Journal of the American Chemical Society
• 出版年：2007
• 出版时间：December 12, 2007
• 年：2007
• 卷：129
• 期：49
• 页码：15128 - 15129
• 全文大小：87K
• 年卷期：v.129,no.49(December 12, 2007)
• ISSN：1520-5126

文摘

We report the design, syntheses, and oxidation reactivity of a new family of non-heme iron pyrrole complexes. The most reactive congener is capable of activating N₂O, an appealing yet challenging oxidant, for oxygen atom transfer. The first generation tpa^PhFe complex reacts with oxygen atom donors to generate a ligand hydroxylated species by intramolecular C-H activation and oxygenation. The second-generation tpa^MesFe system expands on this reactivity to intermolecular hydrogen atom abstraction chemistry through N₂O activation. The observation of arene C-H hydroxylation and the consumption of external hydrogen atom donors implicates a potent metal-centered oxidant, likely an iron(IV)-oxo species, along these reaction pathways. This work establishes a new coordination platform for high-valent iron reactivity.