Cowley Ryan E, Bill Eckhard, Neese Frank, Brennessel William W, Holland Patrick L
Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
Inorg Chem. 2009 Jun 1;48(11):4828-36. doi: 10.1021/ic900001y.
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.
本文描述了（β-二酮亚胺基）铁配合物上四氮烯配体的氧化还原化学。将1-金刚烷基叠氮化物添加到铁（I）源中，最有可能通过亚氨基铁（III）中间体得到四氮烯配合物L（Me）Fe（AdNNNNAd）。对该四氮烯配合物进行的光谱、磁性、晶体学和计算研究表明，一个未成对自旋占据主要基于配体的轨道，并与高自旋铁（II）离子发生反铁磁耦合，从而产生S = 3/2的基态。在配体单占据分子轨道（SOMO）处发生可逆单电子还原，得到双阴离子四氮烯配体，而金属的氧化态和自旋态保持不变。
