Electronic ménages a trois: A molecular orbital perspective of protonated ferryl intermediates and synthetic models

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• 作者：Jeanet Conradie ; Ingar Wasbotten and Abhik Ghosh
• 关键词：Compound II ; High-valent ; Iron ; Alkoxide ; Thiolate ; Phenolate ; Hydroperoxide
• 刊名：Journal of Inorganic Biochemistry
• 出版年：2006
• 出版时间：April 2006
• 年：2006
• 卷：100
• 期：4
• 页码：502-506
• 全文大小：528 K

文摘

Presented here is a molecular orbital perspective of various S = 1 iron(IV)-hydroxo compound II intermediates as well as of synthetic heme and nonheme analogues. A key conceptual issue concerns how the iron(IV) center in these species coexists with highly reducing alkoxide, thiolate, phenolate, and hydroperoxide ligands. We suggest that a clue to this conundrum involves a three-way splitting of the spin density among the iron and two π-basic ligands, which effectively delocalizes the high positive charge away from the iron.