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Updated: Jul 5, 2026

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate
Published on: February 23, 2016
Oxygen-oxygen bond homolysis in a novel titanium(IV) alkylperoxide complex, Cp2Ti(OOtBu)Cl
Antonio G DiPasquale1, Werner Kaminsky, James M Mayer
1Department of Chemistry, Campus Box 351700, University of Washington, Seattle, Washington 98195-1700, USA.
Abstract:
Cp2TiCl2 reacts with NaOOtBu to form the new titanium peroxide complex, Cp2Ti(OOtBu)Cl (1), which has been characterized both in solution and in the solid state. This complex is surprisingly unreactive towards olefins and phosphines, as it does not directly transfer an oxygen atom. Instead, decomposition occurs via initial homolysis of the oxygen-oxygen bond, yielding a tert-butoxyl radical. Decomposition of 1 in the presence of phosphines yields either phosphine oxides (e.g., OPPh3) or phosphinites (e.g., tBuOPEt2), products that result from tBuO* + PR3. O-O bond homolysis is surprising because the Ti(IV) center is d0 and cannot be oxidized, where all previous clear examples of homolytic cleavage of metal peroxide complexes are facilitated by oxidation of the metal center.
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