The First Coordination Polymers Based on 1,3‐Diphosphaferrocenes and 1,1′,2,3′,4‐Pentaphosphaferrocenes†

Phosphaferrocenes in combination with coinage metal salts proved to be excellent building blocks in supramolecular chemistry for the buildup of oligomeric and polymeric assemblies. The synthesis of a series of novel phosphaferrocenes containing the 1,3-P2C3iPr3 and/or the 1,2,4-P3C2iPr2 ligand is described herein. The self-assembly processes of the 1,3-diphospha-, 1,2,4-triphospha-, and 1,1',2,3',4-pentaphosphaferrocenes with CuI halides led to the formation of 1D or 2D polymers. With [Cp*Fe(η5-P2C3iPr3)] (Cp* = η5-C5Me5), infinite chains are formed, whereas with [(η5-P3C2iPr2)Fe(η5-P2C3iPr3)] 1D ladderlike structures are obtained. These are the first polymers containing such a di- and pentaphosphaferrocene, respectively. On the other hand, the use of [Cp*Fe(η5-P3C2iPr2)] leads to the construction of 2D networks with intact sandwich complexes, which is uncommon for this class of complexes.