Iron(II) Complexes with Redox-Active Tetrazene (RNNNNR) Ligands
Iron(II) Complexes with Redox-Active Tetrazene (RNNNNR) Ligands
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DOI：
10.1021/ic900001y
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发表时间：
2009-06-01
影响因子：
4.6
通讯作者：
Holland, Patrick L.
中科院分区：
文献类型：
--
作者：
Cowley, Ryan E.;Bill, Eckhard;Holland, Patrick L.
本文描述了（β-二酮亚胺）铁配合物上四氮烯配体的氧化还原化学。将 1-金刚烷基叠氮化物加成到铁 (I) 源中，最有可能通过亚胺铁 (III) 中间体生成四氮烯配合物 L(Me)Fe(AdNNNNAd)。对四氮烯配合物的光谱、磁性、晶体学和计算研究表明，一个不成对的自旋占据主要基于配体的轨道，并与高自旋铁 (II) 离子反铁磁耦合，产生 S = 3/2 基态。可逆的单电子还原发生在配体单占据分子轨道（SOMO）处，提供双阴离子四氮烯配体，同时保持金属氧化态和自旋态不变。
This paper describes the redox chemistry of a tetrazene ligand on (beta-diketiminato) iron complexes. Addition of 1-adamantyl azide to an iron(I) source gives the tetrazene complex L(Me)Fe(AdNNNNAd), most likely through an imidoiron(III) intermediate. Spectroscopic, magnetic, crystallographic, and computational investigations of the tetrazene complex show that one unpaired spin occupies a primarily ligand-based orbital, and is antiferromagnetically coupled to a high-spin iron(II) ion to give an S = 3/2 ground state. Reversible single-electron reduction occurs at the ligand singly occupied molecular orbital (SOMO), affording a dianionic tetrazene ligand while leaving the metal oxidation state and spin state unchanged.