Utilization of a diamide-diimine (dadi) ligand has permitted the synthesis of various (dadi)TiL (1-L; L = THF, phosphines, R-, etc.), (dadi)Ti=Y (2-Y; Y = O, NR, etc.), and (dadi)TiX2 (3-X2; X = halide). Treatment of 1-THF with RX leads to products likely derived from radical chains, but with the dadi unit directly involved in bond formation due to its redox non-innocence. While some reactions of 2-NAd (Ad = adamantyl), such as the catalytic carbonylation of AdN3 to AdNCO, are consistent with imide-like reactivity, others provide evidence of imidyl character and redox non-innocence of the dadi ligand. Related rearrangements of 3-X2 are also consistent with radical character at both the ligand and metal. A general overview of the system will be presented.

Radical-type reactivity derived from redox non-innocence in the (dadi)Ti(L/X) system

254th National Meeting (2017)

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