How do corroles stabilize high valent metals?
How do corroles stabilize high valent metals?
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DOI：
10.1080/02603590600666256
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发表时间：
2006-01-01
影响因子：
5.4
通讯作者：
Gray, Harry B.
中科院分区：
文献类型：
--
作者：
Gross, Zeev;Gray, Harry B.
三阴离子腐蚀剂很容易被氧化，但它们能够在高氧化态下稳定金属。为了解决这个明显的谜题，我们通过对已有的实验数据的分析，估算了金属d和corole pi的轨道能量。虽然Corole pi轨道的能量比紧密相关的孔道轨道的高，但d轨道的能量甚至更高，这是因为相对刚性的大环三阴离子-配体骨架大大增强了成键。了解Corole pi和a效应的相对重要性有助于了解金属配位的稳定性和反应性，这反过来将进一步推动这一化学热点领域的发展。
Trianionic corroles are readily oxidized, yet they are able to stabilize metals in high oxidation states. In an attempt to solve this apparent puzzle, we have estimated both metal d and corrole pi orbital energies by analysis of well established experimental data. Although the corrole pi orbitals are at higher energies than those of closely related porphy-rins, the d orbital energies are even higher, owing to greatly enhanced a bonding dictated by the relatively rigid macrocyclic trianionic-ligand framework. Understanding the relative importance of corrole pi and a effects sheds new light on metallocorrole stability and reactivity that in turn will further advance this hot area of chemistry.