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β-Diketiminate ligands featuring backbone NMe 2 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 E II /E IV redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NH 2 R)] + (R = H,  Bu) - which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)] + via a proton-shuttling mechanism.

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