Gross Z
Department of Chemistry and Institute of Catalysis Science and Technology, Technion, Haifa, Israel.
J Biol Inorg Chem. 2001 Sep;6(7):733-8. doi: 10.1007/s007750100273.
This commentary concentrates on corrole complexes with the three metal ions that are most relevant to oxidation catalysis: chromium, manganese, and iron. Particular emphasis is devoted to the only recently introduced meso-triarylcorroles and a comparison with the traditionally investigated beta-pyrrole-substituted corroles. Based on a combination of spectroscopic methods, electrochemistry, and X-ray crystallography, it is concluded that in most high-valent metallocorroles the corrole is not oxidized. Both experimental (for (oxo)chromium(V) corrole) and computational (for (oxo)manganese(V) corrole) evidence indicate that the stabilization of high-valent metal ions by corroles originates from a combination of short metal-nitrogen bonds and large metal out-of-plane displacements in the corrole, which lead to quite unexpected interactions of the oxo-metal pi* orbitals with the in-plane orbitals of the corrole.
本评论聚焦于与氧化催化最相关的三种金属离子形成的卟吩配合物:铬、锰和铁。特别强调了最近才引入的中位三芳基卟吩,并将其与传统研究的β-吡咯取代卟吩进行比较。基于光谱方法、电化学和X射线晶体学的综合研究,得出结论:在大多数高价金属卟吩中,卟吩并未被氧化。实验证据(对于(氧代)铬(V)卟吩)和计算证据(对于(氧代)锰(V)卟吩)均表明,卟吩对高价金属离子的稳定作用源于金属-氮短键和卟吩中金属平面外大位移的共同作用,这导致氧代金属π*轨道与卟吩平面内轨道产生了相当意外的相互作用。
J Biol Inorg Chem. 2001-9
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