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3 ligand. Moreover, the complex protonated anywhere can react at several positions, which tremendously increases the number of isomers to be taken into account in a systematic study. With finite computational resources, we have been able to investigate the influence of protonation at the cis position and olefin attack at the trans position of the protonated peroxo moiety (Scheme 1). We chose this approach since the protonation at the peroxo moiety will have the strongest effect on the energy of the σ*(O-O) orbital.
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The most significant influence of the solvent can be expected for the protonated complexes. Since TS 5 is larger than reactant 5 and the positive total charge is therefore better stabilized in TS 5 than in 5, the activation energy will probably be underestimated. Furthermore, the presence of the counterion might increase the activation barrier.
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