Reactivity of the pentelidene complexes [Cp*E{W(CO)5}2] (E = P, As) towards dichalcogenides and chalcogenols - synthesis of novel chalcogenopentelidene 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, Se, Te; Mes = 2,4,6-trimethylphenyl; Tipp = 2,4,6-triisopropylphenyl) and the chalcogenols PhChH (Ch = S, Se). It has been shown that the formation of new E-Ch bonds proceeds under elimination of the Cp* substituent. The resulting chalcogenopentelidene complexes, which have been isolated and fully characterised, represent a novel class of phosphinidene complexes which can be synthesised through this general synthetic route.

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.