A novel half-sandwich Zr(IV) complex [g 5 :g 1 -N -C 5 (CH 3 ) 4 CH 2 CH 2 N(CH 3 ) 2 ]ZrCl 3 (6) together with zirconocene dichlorides [g 5 -C 5 (CH 3 ) 4 CH 2 CH 2 N(CH 3 ) 2 ][g 5 -C 5 (CH 3 ) 5 ]ZrCl 2 (4) and [g 5 -C 5 (CH 3 ) 4 CH 2 CH 2 N(CH 3 ) 2 ] 2 ZrCl 2 (5) have been prepared. Complex 6 has been isolated and characterized in three different forms, namely, as an adduct with THF 6a, an adduct with tetrahydrothiophene 6b, and a solvent-free form 6c. Molecular structures of complexes 4, 6b, and 6c have been established by X-ray diffraction analysis. Complex 6c has been shown to be a monomeric solvent-free half sandwich Zr(IV) complex. The dynamic behavior of complex 6a in a non-solvating medium (an equilibrium between 6a and 6c along with a degenerate interconversion of the Zr-C cp -CH 2 -CH 2 -N(CH 3 ) 2 -(Zr) pseudo-five-member metallacycle) have been studied by the variable-temperature 1 H and 13 C{ 1 H} NMR spectroscopy. The activation parameters for the degenerate five-member cycle interconversion have been elucidated.

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