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 Zr^IV complexes were prepared: tetramethyl(2-methylthioethyl)cyclopentadienylltriclllorozirconium (3), bistetramethyl(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 SZr 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.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 984–992, April, 1996.