Visible-light photolytic synthesis of multinuclear and dendritic iron-nitrile cationic complexes

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.