Rare-Earth Metal Diimide Complexes via Alkylaluminate Templating, Including a Ceric Derivative.
Rare-Earth Metal Diimide Complexes via Alkylaluminate Templating, Including a Ceric Derivative.
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DOI：
10.1002/chem.201805143
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发表时间：
2018-12
期刊：
影响因子：
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通讯作者：
Renita Thim;Dorothea Schädle;C. Maichle‐Mössmer;R. Anwander
中科院分区：
文献类型：
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作者：
Renita Thim;Dorothea Schädle;C. Maichle‐Mössmer;R. Anwander
镧系元素三（四甲基铝酸酯）与两当量的2，6-二异丙基苯胺的质子分解得到LaIII和CeIII二酰亚胺化合物Ln[（μ-NC 6 H3 iPr 2 - 2，6-AlMe 2]（thf）4，其特征在于双齿AlMe 2-连接的二酰亚胺配体。如对于相应的Ce（GaMe 4）3 -反应所揭示的，二酰亚胺络合物的形成经由[Ce{（μ-NC 6 H3 iPr 2 - 2，6）（HNC 6 H3 iPr 2 - 2，6）（MMe 3）}]2（Me=Al，Ga）类型的四金属络合物进行。氧化的铈（III）配合物与六氯乙烷导致中性CeIV二酰亚胺物种。部分质子分解与苯乙炔和氢解通过H3 SiPh给结论性的见解，这样的二酰亚胺配合物的反应性配位位点。
Protonolysis of lanthanide tris(tetramethylaluminate)s with two equivalents of 2,6-diisopropylaniline affords LaIII and CeIII diimide compounds Ln[(μ-NC6 H3 iPr2 -2,6)2 AlMe2 ](thf)4 featuring a bidentate AlMe2 -linked diimido ligand. As revealed for the corresponding Ce(GaMe4 )3 -reaction, formation of the diimide complexes proceeds via tetrametallic complexes of the type [Ce{(μ-NC6 H3 iPr2 -2,6)(HNC6 H3 iPr2 -2,6)(MMe3 )}]2 (Me=Al, Ga). Oxidation of the cerium(III) complex with hexachloroethane leads to a neutral CeIV diimide species. Partial protonolysis with phenylacetylene and hydrogenolysis via H3 SiPh give conclusive insights into the reactive coordination sites of such diimide complexes.