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An Isolable Azide Adduct of Titanium(II) Follows Bifurcated Deazotation Pathways to an Imide

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Title
An Isolable Azide Adduct of Titanium(II) Follows Bifurcated Deazotation Pathways to an Imide
Author(s)
Anders Reinholdt; Kwon, Seongyeon; Jafari, Mehrafshan G.; Gau, Michael R.; Caroll, Patrick J.; Lawrence, Chad; Gu, Jun; Mu-Hyun Baik; Mindiola, Daniel J.
Publication Date
2022-01
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.144, no.1, pp.527 - 537
Publisher
AMER CHEMICAL SOC
Abstract
AdN3 (Ad = 1-adamantyl) reacts with the tetrahedral TiII complex 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(gamma 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 degrees C) is at odds with the large fraction of imide complex formed directly in reactions between AdN3 and [(TptBu,Me)TiCl] at room temperature (similar to 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 pi-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].
URI
https://pr.ibs.re.kr/handle/8788114/11210
DOI
10.1021/jacs.1c11215
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
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