In the reduction of tetramethylethylene-bridged (CH3)4C2(CsH4hTiCI2 under argon, studied by cyclic voltammetry, a first reduction to the Ti III stage occurs at a potential of-0.92 V vs. SCE, close to that of (CsHshTiCI2, and a second reduction to the Ti II stage at a potential of-2.53 V, about 0.3 V more negative than in the corresponding reduction of the unbridged analogue. Decay of the tetramethylethylene-bridged Ti II product is considerably faster than that of its unbridged analogue. Changes induced by the presence of an N2 or H2 atmosphere indicate the occurrence of secondary reactions. In the presence of CO, reduction to (CH3)4C2(CsH4hTi(COh occurs at-2.0 V. This tetramethylethylene-bridged titanocene dicarbonyl complex, which is also formed by reduction of (CH3)4C2(CsH4hTiCI2 with Mg metal under CO, undergoes irreversible reduction and oxidation at-2.78 and-0.08 V, respectively. When the latter process is conducted in the presence of Cl-, the dichloride (CH3)4C2(CsH4hTiCI2 is regenerated.
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