Neutral and Cationic Zinc Complexes with N- and S-Donor-Functionalized Cyclopentadienyl Ligands

Abstract

The synthesis of neutral and cationic zinc cyclopentadienyl (Cp) complexes with amino and thio donor groups that are attached to the Cp ring via a side chain is reported. The amino-functionalized zincocene [ZnCp3N2] (3; Cp3N = C5Me4(CH2)3NMe2) was prepared in a salt metathesis reaction from KCp3N and ZnCl2. In the solid-state structure of 3, which was determined by single-crystal X-ray diffraction, one of the Cp3N ligands is coordinated as a chelating ligand through a ring carbon atom and through the amino group, whereas the other Cp3N ligand is bound in a monodentate mode through the Cp ring only. A reaction of 3 with ZnEt2, [ZnCp*2] (Cp* = C5Me5), and [ZnCp2N2] (2; Cp2N = C5Me4(CH2)2NMe2) gave the heteroleptic complexes [ZnEtCp3N] (4), [ZnCp*Cp3N] (5), and [ZnCp3NCp2N] (6), respectively. The incorporation of a second amino group in the same side chain led to the formation of the mononuclear zinc chlorido complex [ZnClCptmeda] (7; Cptmeda = C5Me4(CH2)2NMe(CH2)2NMe2), in which the Cptmeda ligand is bound ...