Tetramethyl(2-methylthioethyl)cyclopentadienyl complexes of zirconium(IV): Synthesis, crystal structure, and dynamic behavior in solutions

Chelating sulfur-containing cyclopentadienyl ligand tetramethyl(2-methylthioethyl)cyclopentadiene (1), was synthesized for the first time. Its sodium (2a) and lithium (2b) derivatives were isolated in the crystalline state. Starting from compound1 some novel ZrIV complexes were prepared: [tetramethyl(2-methylthioethyl)cyclopentadienylltriclllorozirconium (3), bis[tetramethyl(2-methylthioethyl)cyclopentadienylldichlorozirconium (4), and [pentamethylcyclopentadienyll [tetramethyl(2-methylthioethyl)cyclopentadienylldichlorozirconium (5). The crystal structures of3 and5 were determined by X-ray diffraction analysis. The dynamic behavior of complex3 in various solvents was investigated by1H and13C N MR spectroscopy. The S→Zr coordination bond was shown to exist in complex3 both in the crystalline state and in solution. No coordination of this type was found in compounds4 and5.