Zirconium-91 chemical shifts and line widths as indicators of coordination geometry distortions in zirconocene complexes

Article abstract of DOI:10.1021/om950757c

⁹¹Zr NMR chemical shifts and line widths (Δυ_1/2) are reported for a number of ring-bridged and ring-substituted zirconocene dichloride, dibromide, and dimethyl complexes. Ab initio computations at the SCF level employing basis sets of moderate size suggest that the magnitude of the electric field gradient (EFG) at the Zr atom dominates Δυ_1/2 when the substituents X at Zr are varied (X = Br, Cl, Me). Substituents at the cyclopentadiene (Cp) rings affect the computed EFGs much less; in these cases, the line widths Δυ_1/2 are governed by the molecular correlation times τ_c, which were obtained for several zirconocene dichlorides from T₁(¹³C) measurements. Experimental trends in δ(⁹¹Zr) of zirconocenes are well reproduced computationally with the IGLO (individual gauge for localized orbitals) or GIAO (gauge including atomic orbitals) SCF methods employing large basis sets. Model calculations suggest that δ(⁹¹Zr), as well as the EFG, are quite sensitive to the inclination and twist angles of the Cp rings and, to a lesser extent, to the CpZrCp′ angle. A substantial deshielding, δ(⁹¹Zr) ca. 700 ppm, is predicted for (C₅H₅)₂ZrMe⁺, presumably the active olefin-polymerizing catalyst.