Baglia Regina A, Prokop-Prigge Katharine A, Neu Heather M, Siegler Maxime A, Goldberg David P
Department of Chemistry, The Johns Hopkins University , 3400 North Charles Street, Baltimore, Maryland 21218, United States.
J Am Chem Soc. 2015 Sep 2;137(34):10874-7. doi: 10.1021/jacs.5b05142. Epub 2015 Aug 21.
Isomorphous crystals of Mn(V)(O) and Cr(V)(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.
通过单晶X射线衍射对Mn(V)(O)和Cr(V)(O)咕啉的同构晶体进行了表征。与氢原子供体和分离的质子耦合电子转移试剂的反应性研究表明,这两种配合物在氢原子提取能力上存在显著差异。隐含的驱动力的巨大差异与氧化还原电位的趋势相反,这表明碱性是决定相同配体环境中两种金属氧物种反应性显著差异的关键因素。