| Abstract
| - Reactions of d0 amides M(NMe2)4 (M = Zr, 1; Hf, 2) with O2 have been found to yield unusualtrinuclear oxo aminoxide complexes M3(NMe2)6(μ-NMe2)3(μ3-O)(μ3-ONMe2) (M = Zr, 3; Hf, 4) in high yields.Tetramethylhydrazine Me2N−NMe2 was also observed in the reaction mixtures. Crystal structures of 3and 4 have been determined. Density functional theory calculations have been performed to explore themechanistic pathways in the reactions of model complexes Zr(NR2)4 (R = H, 5; Me, 1) and [Zr(NR2)4]2(R = H, 5a; Me, 1a) with triplet O2. Monomeric and dimeric reaction pathways in the formation of the Zrcomplex 3 are proposed.
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