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• W2057309790 endingPage "328" @default.
• W2057309790 startingPage "323" @default.
• W2057309790 abstract "Redox properties of the substituted zirconocene dichlorides: (C5H5−nMen)2 ZrCl2 (n=0–5), [C5H5−n(SiMe3)n]2ZrCl2 (n=0–3), [C5Me4(SiMe3)](C5HMe4)ZrCl2 and two ansa-analogues Me2Si(C5H4)2ZrCl2 and Me2Si[C5H2(SiMe3)2]2ZrCl2 were investigated by cyclic voltammetry on a mercury electrode in tetrahydrofuran. In the (C5H5−nMen)2ZrCl2 (n=0–4) compounds, standard electrode potential (E°) of the one-electron uptake shifts to more negative values by 0.071 V per one methyl group. A deviation from this linear dependence to a less negative E° is observed for (C5Me5)2ZrCl2. This effect is attributed to the steric hindrance between rotating C5Me5 ligands which tends to decrease the angle between the cyclopentadienyl ring planes (φ) and consequently, the energy difference between MO frontier orbitals. In the trimethylsilylated compounds, the net effect of SiMe3 is negligible, giving virtually the same value of E° for n=0–3. In μ-SiMe2-bridged ansa-compounds the difference in E° of 147 mV corresponds to the negative shift of 37 mV per one SiMe3 group. Owing to the rigid angle φ, this shift can be tentatively accounted for the electronic effect of the SiMe3 groups. In the non-ansa-compounds, the negative shift due to the electronic effect of SiMe3 groups is assumed to be roughly compensated by a positive shift resulting from a sterically controlled diminution of φ." @default.
• W2057309790 created "2016-06-24" @default.
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• W2057309790 date "1999-07-01" @default.
• W2057309790 modified "2023-10-18" @default.
• W2057309790 title "Cyclic voltammetry of methyl- and trimethylsilyl-substituted zirconocene dichlorides" @default.
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• W2057309790 doi "https://doi.org/10.1016/s0022-328x(99)00170-9" @default.
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