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. A synthetic approach to a series of iPr‐substituted phosphaferrocenes was found. Their self‐assembly with CuI halides led to one‐ and two‐dimensional polymers: 1D chains containing the 1,3‐diphosphaferrocene, 1D ladderlike structures with the 1,1′,2,3′,4‐pentaphosphaferrocene, and 2D meshlike networks bearing the 1,2,4‐triphosphaferrocene.