Spitzer Fabian, Balázs Gábor, Graßl Christian, Keilwerth Martin, Meyer Karsten, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93040, Regensburg, Germany.
Friedrich-Alexander University Erlangen-Nürnberg (FAU), Department of Chemistry and Pharmacy, Inorganic Chemistry, Egerlandstrasse 1, 91058, Erlangen, Germany.
Angew Chem Int Ed Engl. 2018 Jul 9;57(28):8760-8764. doi: 10.1002/anie.201802888. Epub 2018 Jun 8.
In a systematic study of the activation of As , three [LCo(tol)] (L=β-diiminato) complexes have revealed different steric and electronic influences. 2,6-Diisopropylphenyl (Dipp) and 2,6-dimethylphenyl (dmp) flanking groups were used, one of the ligands with H backbone substituents (β-dialdiminate L ) and two with Me substituents (β-diketiminates L and L ). In the reaction with As , different dinuclear products [(LCo) As ] (LM=L (1), L (2), L (3)) were isolated, with all showing differently shaped [Co As ] cores in the solid state: octahedral in 1, prismatic in 2, and asterane-like in 3. Thermal treatment of 3 leads to the abstraction of one arsenic atom to yield [(L Co) As ] (4). All products were comprehensively characterized by single-crystal X-ray diffraction, FD-MS, and H NMR spectroscopy. A rational explanation for the different reactivity is also proposed and DFT calculations shed light on the nature of the highly flexible [Co As ] cores.
在一项关于砷活化的系统研究中，三种[LCo(tol)]（L = β - 二亚胺基）配合物展现出了不同的空间和电子影响。使用了2,6 - 二异丙基苯基（Dipp）和2,6 - 二甲基苯基（dmp）侧翼基团，其中一种配体带有氢骨架取代基（β - 二醛亚胺基L ），另外两种带有甲基取代基（β - 二酮亚胺基L 和L ）。在与砷的反应中，分离出了不同的双核产物[(LCo)₂As]（LM = L (1)、L (2)、L (3)），所有产物在固态下均呈现出形状各异的[Co₂As]核：1为八面体，2为棱柱体，3为类海星烷。对3进行热处理会导致一个砷原子被提取出来，生成[(L'Co)₂As]（4）。所有产物均通过单晶X射线衍射、FD - MS和¹H NMR光谱进行了全面表征。还对不同的反应活性提出了合理的解释，并且DFT计算揭示了高度灵活的[Co₂As]核的性质。
