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Reduction of organic azides by indyl-anions. Isolation and reactivity studies of indium-nitrogen multiple bonds.

ABSTRACT: The synthesis of a new potassium-indyl complex, K[In(NON^Ar)] (NON^Ar = [O(SiMe₂NAr)₂]^2-, Ar = 2,6-ⁱPr₂C₆H₃) and its reactivity with organic azides RN₃ is reported. When R = 2,6-bis(diphenylmethyl)-4- ^t Bu-phenyl, a dianionic alkyl-amide ligand is formed via C-H activation across a transient In-N_imide bond. Reducing the size of the R-group to 2,4,6-trimethylphenyl (mesityl, Mes) enables oxidation of the indium and elimination of dinitrogen to afford the imide species, K[In(NON^Ar)(NMes)]. The anion contains a short In-N_imide bond, shown computationally to contain appreciable multiple bond character. Reaction of isolated imides with an additional equivalent of azide (R = Mes, SiMe₃) generates tetrazenido-indium compounds K[In(NON^Ar){?-N,N'-N₄(Mes)(R)-1,4}], shown by X-ray crystallography to contain planar InN₄ heterocycles in the anion.

SUBMITTER: Anker MD

PROVIDER: S-EPMC6349055 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Reduction of organic azides by indyl-anions. Isolation and reactivity studies of indium-nitrogen multiple bonds.

Anker Mathew D MD Lein Matthias M Coles Martyn P MP

Chemical science 20181112 4

The synthesis of a new potassium-indyl complex, K[In(NONAr)] (NONAr = [O(SiMe2NAr)2]2-, Ar = 2,6-iPr2C6H3) and its reactivity with organic azides RN3 is reported. When R = 2,6-bis(diphenylmethyl)-4- t Bu-phenyl, a dianionic alkyl-amide ligand is formed via C-H activation across a transient In-Nimide bond. Reducing the size of the R-group to 2,4,6-trime ...[more]

PMID: 30774921

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