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‐P2C3 iPr3 and/or the 1,2,4‐P3C2 iPr2 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‐P2C3 iPr3)] (Cp* = η5‐C5Me5), infinite chains are formed, whereas with [(η5‐P3C2 iPr2)Fe(η5‐P2C3 iPr3)] 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‐P3C2 iPr2)] leads to the construction of 2D networks with intact sandwich complexes, which is uncommon for this class of complexes.

Pentelidene complexes of the type [Cp*E{W(CO)5}2] (Cp* = C5Me5; 1a: E = P, 1b: E= As) were reacted with the dichalcogenides R2Ch2 (R = Ph, Mes, Tipp; Ch = S,...

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Stibinidene complexes are rare and highly sensitive low-valent main group compounds, which have not been studied extensively for their reaction behavior so far. In the reaction with GaCl 3, the stibinidene complex [ClSb{Cr(CO) 5 } 2 (thf)] (1) shows a dimerization to [ClSb{Cr(CO) 5 } 2 ] 2 (2) and yields the anionic double-chlorinated compound [Cl 2 Sb{Cr(CO) 5 } 2 ] À (3) in the reaction with different ionic nucleophiles. When using neutral nucleophiles (such as amines, isocyanides and phosphines) as reaction partners, tetrahedral complexes of the type [ClSb {Cr(CO) 5 } 2 Nu] (4: Nu = NH 2 Mes; 5: Nu = CN(dmp); 6: Nu = PPh 3 ; 7: Nu = PPh 2 H) are formed which can be used in subsequent reactions. All of these products are among the first of their type to be synthesized and isolated.