Ornelas Cátia, Ruiz Jaime, Rodrigues João, Astruc Didier
Institut des Sciences Moléculaires, UMR CNRS No 5255, Université Bordeaux 1, 351 Cours de la Libération, 33405 Talence Cedex, France.
Inorg Chem. 2008 May 19;47(10):4421-8. doi: 10.1021/ic800100k. Epub 2008 Mar 21.
Multinuclear and dendritic iron-nitrile piano-stool cationic complexes were synthesized in quantitative yield by a single-step synthesis involving visible-light photolysis of the complex [CpFe(eta(6)-toluene)][PF6]. This synthetic strategy was applied to mono-, bis- and tris-nitrile ligands and to new nitrile-terminated dendrimers containing 9, 27, and 81 tethers. All the synthesized products are deep red solids or red waxy products, highly stable to air and moisture. They were characterized by (1)H, (13)C, and (31)P NMR, elemental analysis, UV-vis spectroscopy, and cyclic voltammetry (single reversible oxidation wave to Fe(III)). Only the para-disubstituted arene dinitrile diiron complex shows two separated reversible waves indicating some electronic communication between the iron centers through the nitrile ligands.
通过单步合成法，利用配合物[CpFe(η(6)-甲苯)][PF6]的可见光光解反应，以定量产率合成了多核和树枝状铁-腈钢琴凳阳离子配合物。这种合成策略应用于单腈、双腈和三腈配体以及含有9、27和81个连接基团的新型腈基封端树枝状大分子。所有合成产物均为深红色固体或红色蜡状产物，对空气和水分具有高度稳定性。通过1H、13C和31P NMR、元素分析、紫外-可见光谱和循环伏安法（Fe(III)的单可逆氧化波）对其进行了表征。只有对二取代芳烃二腈二铁配合物显示出两个分离的可逆波，表明铁中心之间通过腈配体存在一些电子通讯。
