Do Dinh Cao Huan, Protchenko Andrey V, Fuentes M Ángeles, Hicks Jamie, Vasko Petra, Aldridge Simon
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Chem Commun (Camb). 2020 Apr 30;56(34):4684-4687. doi: 10.1039/d0cc00875c. Epub 2020 Mar 25.
β-Diketiminate ligands featuring backbone NMe 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/E redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NHR)] (R = H, Bu) - which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)]via a proton-shuttling mechanism.
具有主链NMe基团的β-二酮亚胺配体已被用于制备一系列[(N-萘二甲酰亚胺)E]型（E = Si、Ge、Sn）的二配位阳离子，并对其与N-H键的反应活性进行了研究。虽然较重的第14族体系通过简单加合物的形成进行反应，但对于E = Si会发生N-H氧化加成，这与E/E氧化还原电位的差异一致。结构表征的Ge/Sn加合物可被视为相应（瞬态）Si体系[(N-萘二甲酰亚胺)Si·(NHR)]（R = H、Bu）的模型——这些体系是通过质子穿梭机制形成[(N-萘二甲酰亚胺)Si(H)(NHR)]的潜在中间体。
