Synthesis and structures of new binuclear zinc alkyl, aryl and aryloxo complexes

The synthesis of a series of binuclear zinc complexes with Cl, N and O bridges is reported. The reaction of EtZnCl with B(C 6F 5) 3 in the presence of hexamethylbenzene affords the arene complex [Zn(μ-Cl)(C 6F 5)(η-C 6Me 6)] 2 in which the C 6Me 6 ligand may be regarded as η 3-bonded. The comproportionation of Zn[N(SiMe 3) 2] 2 with ZnBu t 2 or Zn(C 6F 5) 2 · toluene gave [Bu tZn{μ-N(SiMe 3) 2}] 2 and [C 6F 5Zn{μ-N(SiMe 3) 2}] 2, respectively, with three-coordinate zinc. The reaction of ZnEt 2 with C 6F 5OH in the presence of pyridine gave [EtZn(μ-OC 6F 5)(py)] 2, while ZnMe 2 and C 6F 5OH followed by recrystallisation from THF gave [Zn(OC 6F 5)(μ-OC 6F 5)(THF) 2] 2 with five-coordinate zinc in a trigonal-bipyramidal geometry. The structures of these compounds have been determined.