Mehrkernige CpZr(IV)- und CpHf(IV)-Komplexe mit Oximatobrücken

W olfgang B raunw arth , U lf T hew alt* Sektion Röntgenund Elektronenbeugung der Universität Ulm, D-89069 Ulm Z. Naturforsch. 52b, 1011-1018 (1997); eingegangen am 4. März 1997 Zirconium Complexes, Hafnium Complexes, Oximato Ligands, Oxime Ligand, Molecular Structure The mono-cyclopentadienyl metal complexes CpZrCl3(dme) and CpHfCl3(dme) react with acetone oxime in the presence of triethylamine to form the isotypic dinuclear complexes [CpMCl2]2(M-ONCMe2)2(//-HONCMe2) (1: M = Zr; 2: M = Hf). 1 and 2 contain two oximato bridges and one oxime bridge. In the presence of water the reaction gives, with partial hydro­ lysis, the cyclic trinuclear compounds [CpZrCl]3(a3-0)(M3-0H )(«-0N C M e2)3«/:Me2C N 0H (3) and [CpHfCl]3(M3-0)(M3-Cl)(//-0NCMe2)3*CH2Cl2 (4). In 1 to 4 the bridging oximato groups are side-on bonded via O and N to one metal atom and via (only) O to the other metal atom. The metal atoms of 1 to 4 exhibit an 18-electron configuration.