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

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. [ABSTRACT FROM AUTHOR]