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N–H cleavage vs. Werner complex formation: reactivity of cationic group 14 tetrelenes towards amines

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Abstract

β-Diketiminate ligands featuring backbone NMe2 groups have been exploited to access a series of two-coordinate cations of the type [(N-nacnac)E]+ (E = Si, Ge, Sn), whose reactivity towards N–H bonds has been investigated. While the heavier group 14 systems react via simple adduct formation, N–H oxidative addition occurs for E = Si consistent with differences in EII/EIV redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NH2R)]+ (R = H, tBu) – which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)]+ via a proton-shuttling mechanism.

Graphical abstract: N–H cleavage vs. Werner complex formation: reactivity of cationic group 14 tetrelenes towards amines

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Article information


Submitted
03 Feb 2020
Accepted
16 Mar 2020
First published
16 Mar 2020

Chem. Commun., 2020, Advance Article
Article type
Communication

N–H cleavage vs. Werner complex formation: reactivity of cationic group 14 tetrelenes towards amines

D. C. H. Do, A. V. Protchenko, M. Á. Fuentes, J. Hicks, P. Vasko and S. Aldridge, Chem. Commun., 2020, Advance Article , DOI: 10.1039/D0CC00875C

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