Synthetic and Structural Study on Orthometallated Ferrocene Complexes: Non‐Planar Metallabenzene and Five‐Membered Metallacycle Complexes with Closed Os ₃3 Triangles

摘要

> Thermolysis of ( Z )‐1‐ferrocenyltelluro‐1‐ferrocenyl‐4‐ferrocenyl‐1‐buten‐3‐yne with [Os ₃ (CO) ₁₂ ] in toluene gave two new clusters: non‐planar six‐membered metallacycle complex [Os ₃ H(CO) ₇ (μ ₃ ‐Te){η 1 :η 1 :η 2 :η 2 ‐FcCCC(H)(Fc) ₂ }] ( 1 , Fc = ferrocenyl) and five‐membered cyclometallated ring complex [Os ₃ (CO) ₇ (μ ₃ ‐Te){η 1 :η 1 :η 3 ‐FcC(H)C(H)CC(Fc) ₂ }] ( 2 ). Compounds 1 and 2 may be thought to form by orthometallation of ferrocene with a closed Os ₃ triangle by intramolecular rearrangement of atoms within the cluster complexes. Typically the formation of a non‐planar metallabenzene such as 1 may involve the orthometallation of another aromatic ring. Also, conversion of 1 to 2 shows the initial step required for alkene hydrogenation by a tellurium‐bridged triosmium cluster. Both compounds were characterized by IR and 1 H NMR spectroscopy, and their structures established by single‐crystal XRD.