Highly Electron-Rich ß-Diketiminato Systems: Synthesis and Coordination Chemistry of Amino-Functionalized "N-nacnac" Ligands.
Highly Electron-Rich ß-Diketiminato Systems: Synthesis and Coordination Chemistry of Amino-Functionalized "N-nacnac" Ligands.
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高度富含电子的 à-Diketiminato 系统：氨基官能化“N-nacnac”配体的合成和配位化学。
DOI：
10.1002/chem.201700757
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发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Do DCH
中科院分区：
文献类型：
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作者：
Do DCH
报道了一类富电子氨基功能化的β-二酮亚胺（N-nacnac）配体的合成，其中两种合成方法已被开发用于具有骨架NMe 2或NEt 2基团和一系列N-结合芳基取代基的系统。与它们的（Nacnac）H对应物相比，质子配体的结构特征在于双（亚胺）互变异构体和主链CH 2基团。与锂、镁或铝烷基的直接金属化允许通过亚甲基官能团的去质子化获得相应的金属络合物;在每种情况下，X射线结构与离域亚氨基酰胺配体描述一致。然后利用使用锂N-nacnac络合物的金属转移来获得p-和f-嵌段金属络合物，这允许N-nacnac配体家族与其更熟悉的Nacnac对应物进行类似的基准测试。在SnII的情况下，通过引入骨架NR 2基团而实现的电子扰动的程度似乎受到氨基无法实现与N2 C3杂环的有效缀合的限制。对于更硬的Yb III离子的络合物，观察到与已建立的结构规范更明显的偏离，X射线晶体学证明了azaallyl/亚氨基甚至azaallyl/NMe 2配位模式。
The synthesis of a class of electron‐rich amino‐functionalized β‐diketiminato (N‐nacnac) ligands is reported, with two synthetic methodologies having been developed for systems bearing backbone NMe2or NEt2groups and a range ofN‐bound aryl substituents. In contrast to their (Nacnac)H counterparts, the structures of the protio‐ligands feature the bis(imine) tautomer and a backbone CH2group. Direct metalation with lithium, magnesium, or aluminium alkyls allows access to the respective metal complexes through deprotonation of the methylene function; in each case X‐ray structures are consistent with a delocalized imino‐amide ligand description. Transmetalation using lithiumN‐nacnac complexes is then exploited to access p‐ and f‐block metal complexes, which allow for like‐for‐like benchmarking of theN‐nacnac ligand family against their more familiar Nacnac counterparts. In the case of SnII, the degree of electronic perturbation effected by introduction of the backbone NR2groups appears to be constrained by the inability of the amino group to achieve effective conjugation with the N2C3heterocycle. More obvious divergence from established structural norms is observed for complexes of the harder YbIIion, with azaallyl/imino and even azaallyl/NMe2coordination modes being demonstrated by X‐ray crystallography.