A new tetradentate redox-active ligand, N,N'-bis-(3-dimethylamino-propyl)-4,5-dimethoxy-benzene-1,2-diamide ([N2N2cat]2�), was synthesized and coordinated to titanium(IV) and zirconium(IV) to give the distorted octahedral complexes [N2N2cat]TiCl2 and [N2N2cat]ZrCl2. Cyclic voltammetry revealed [N2N2cat]TiCl2 to be capable of two 1-electron reversible oxidations, while [N2N2cat]ZrCl2 exhibited one coupled, two-electron oxidation. Ligand arm lability was observed in the {[N2N2cat]Ti(=NAr)}2 dimer, and the bis-phenylacetylide complex [N2N2cat]Ti(C=CPh)2 facilitates the reductive elimination of 1,4-diphenylbutadiyne upon oxidation by PhICl2, revealing the ([N2N2cat]M)2+ construct to be potentially useful in chemical transformations.

Steric and electronic consequences of flexibility in a tetradentate redox-active ligand on group IV metals

241st National Meeting (2011)

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