Mn(V)(O) versus Cr(V)(O) Porphyrinoid Complexes: Structural Characterization and Implications for Basicity Controlling H-Atom Abstraction

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• 作者：Regina A. Baglia ; Katharine A. Prokop-Prigge ; Heather M. Neu ; Maxime A. Siegler ; David P. Goldberg
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：September 2, 2015
• 年：2015
• 卷：137
• 期：34
• 页码：10874-10877
• 全文大小：311K
• ISSN：1520-5126

文摘

Isomorphous crystals of Mnp>Vp>(O) and Crp>Vp>(O) corrolazines were characterized by single crystal X-ray diffraction. Reactivity studies with H atom donors and separated PCET reagents show a dramatic difference in H atom abstracting abilities for these two complexes. The implied large difference in driving force is opposite the trend in redox potentials, indicating that basicity is a key factor in determining the striking difference in reactivity for two metal-oxo species in identical ligand environments.