Titanium(III) Trisamidotriazacyclononane:  Reactions with C₆₀ and Radicals

The reaction of titanium trisamidotriazacyclononane, [Ti{N(Ph)SiMe₂}₃tacn] (1), with C₆₀ led to the synthesis of [Ti{N(Ph)SiMe₂}₃tacn]C₆₀ (2) in high yield. Treatment of 2 with PhCH₂Br led to the formation of [Ti{N(Ph)SiMe₂}₃tacn]Br and the radical PhCH₂C₆₀ (3). The reaction of CH₃I with 1 gives two products. One is [Ti{N(Ph)SiMe₂}₃tacn]I (4), which results from the oxidation of 1 by an I radical. The other product, 5, resulting from a multistep reaction scheme that involves redox and nucleophilic reactions, presents an imido ligand formed by ligand rearrangement upon C−N bond cleavage. In solution, an exchange process that corresponds to a reversible 1,3-silyl shift between two Ti-bonded N atoms leads to isomers 5a and 5b. This equilibrium transforms an imido (TiNPh) into an amido ligand (Ti{NPh}SiMe₂CH₂Ph) with concomitant generation of an anionic moiety in the originally neutral triazacyclononane ring. In solution, either 5a or 5b displays additional fluxional processes that consist of its corresponding racemization processes.