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• W4200225388 endingPage "537" @default.
• W4200225388 startingPage "527" @default.
• W4200225388 abstract "AdN3 (Ad = 1-adamantyl) reacts with the tetrahedral TiII complex [(TptBu,Me)TiCl] (TptBu,Me = hydrotris(3-tert-butyl-5-methylpyrazol-1-yl)borate) to generate a mixture of an imide complex, [(TptBu,Me)TiCl(NAd)] (4), and an unusual and kinetically stable azide adduct of the group 4 metal, namely, [(TptBu,Me)TiCl(γ-N3Ad)] (3). In these conversions, the product distribution is determined by the relative concentration of reactants. In contrast, the azide adduct 3 forms selectively when a masked TiII complex (N2 or AdNC adduct) reacts with AdN3. Upon heating, 3 extrudes dinitrogen in a unimolecular process proceeding through a titanatriazete intermediate to form the imide complex 4, but the observed thermal stability of the azide adduct (t1/2 = 61 days at 25 °C) is at odds with the large fraction of imide complex formed directly in reactions between AdN3 and [(TptBu,Me)TiCl] at room temperature (∼50% imide with a 1:1 stoichiometry). A combination of theoretical and experimental studies identified an additional deazotation pathway, proceeding through a bimetallic complex bridged by a single azide ligand. The electronic origin of this deazotation mechanism lies in the ability of azide adduct 3 to serve as a π-backbonding metallaligand toward free [(TptBu,Me)TiCl]. These findings unveil a new class of azide-to-imide conversions for transition metals, highlighting that the mechanisms underlying this common synthetic methodology may be more complex than conventionally assumed, given the concentration dependence in the conversion of an azide into an imide complex. Lastly, we show how significantly different AdN3 reacts when treated with [(TptBu,Me)VCl]." @default.
• W4200225388 created "2021-12-31" @default.
• W4200225388 creator A5008659095 @default.
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• W4200225388 creator A5089534950 @default.
• W4200225388 date "2021-12-28" @default.
• W4200225388 modified "2023-10-10" @default.
• W4200225388 title "An Isolable Azide Adduct of Titanium(II) Follows Bifurcated Deazotation Pathways to an Imide" @default.
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