Abstract
The reaction of the d 1 four-legged piano-stool complexes Cp★MoX 4 (X Cl, Br) with the d 3-d 3 binuclear complexes Cp 2★Mo 2Y 4 (Y Cl, Br, I) results in electron transfer and formation of the salts [Cp 2★Mo 2Y 2] +[Cp★MoX 4] −. Solutions of [Cp 2★Mo 2I 4] +[Cp★MoX 4] − (X Cl, Br) are stable indefinitely in chlorocarbon solvents. However, for the Cp 2★Mo 2Y 4 /Cp★MoX 4 (Y, X Cl, Br) systems, conversion to the complexes Cp 2★Mo 2Y 6- n X n is observed together with halide exchange reactions between the cation and the anion. The formation of Cp 2★Mo 2 Y 6- n X n and the halide exchange are postulated to proceed via a common associative intermediate. The rate of formation of Cp 2★Mo 2Y 6- n X n depends mostly on the Lewis acidity of the cation Cp 2 ★Mo 2Y 4 +, which varies in the order [Cp 2★Mo 2Cl 4] +å[Cp 2★Mo 2Br 4] +å [Cp 2★Mo 2I 4] +, and has little dependence on the nature of X.
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