Structural and spectroscopic characterization of an electrophilic iron nitrido complex
Structural and spectroscopic characterization of an electrophilic iron nitrido complex
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DOI：
10.1021/ja8027372
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发表时间：
2008-08-13
影响因子：
15
通讯作者：
Smith, Jeremy M.
中科院分区：
文献类型：
--
作者：
Scepaniak, Jeremiah J.;Fulton, Meita D.;Smith, Jeremy M.
我们已经分离和结构特征的终端铁氮配合物支持的庞大的三（卡宾）硼酸盐配体。该配合物的电子结构表明，a（1）LUMO（以前的Fe（d（z）2））通过减少与卡宾σ-供体配体的反键相互作用和与更高的Fe 4s和4p原子轨道的构型混合（杂化）而强烈稳定。这种不寻常的成键相互作用导致了具有亲电特性的低位Fe氮化物受体轨道（LUMO）。与PPh 3的反应导致氮原子转移到膦上，支持涉及三苯基膦HOMO在铁氮络合物的亲电LUMO处的亲核攻击的反应机制。
We have isolated and structurally characterized a terminal iron nitrido complex supported by a bulky tris(carbene)borate ligand. The electronic structure of this complex reveals that the a(1) LUMO (formerly Fe(d(z)2)) is strongly stabilized by reduced antibonding interactions with the carbene sigma-donor ligands and configurational mixing (hybridization) with higher lying Fe 4s and 4p atomic orbitals. This unusual bonding interaction results in a low-lying Fe nitrido acceptor orbital (LUMO) that possesses electrophilic character. Reaction with PPh3 results in nitrogen atom transfer to the phosphine, supporting a reaction mechanism involving nucleophilic attack of the triphenylphosphine HOMO at the electrophilic LUMO of the iron nitrido complex.