Reckziegel Alexander, Kour Manjinder, Battistella Beatrice, Mebs Stefan, Beuthert Katrin, Berger Robert, Werncke C Gunnar
Department of Chemistry, Philipps-University Marburg, Hans-Meerwein-Strasse 4, 35032, Marburg, Germany.
Institute of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Strasse 2, 12489, Berlin, Germany.
Angew Chem Int Ed Engl. 2021 Jul 5;60(28):15376-15380. doi: 10.1002/anie.202103841. Epub 2021 Jun 9.
We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L ] , (L=N(Dipp)SiMe ), Dipp=2,6-diisopropylphenyl) with very long Co-N bonds of around 1.75 Å. Their electronic structure was interrogated using a variety of physical and spectroscopic methods such as EPR or X-Ray absorption spectroscopy which leads to their description as highly unusual imidyl cobalt complexes. Computational analyses corroborate these findings and further reveal that the high-spin state is responsible for the imidyl character. Exchange of the Dipp substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me Si shift from the ancillary ligand set to the imidyl nitrogen, revealing a highly reactive, nucleophilic character of the imidyl unit.
我们报道了一系列三角亚胺基钴配合物[Co(NAryl)L ]（L = N(Dipp)SiMe ，Dipp = 2,6 - 二异丙基苯基）的合成，这些配合物具有约1.75 Å的非常长的Co - N键。使用多种物理和光谱方法，如电子顺磁共振（EPR）或X射线吸收光谱对它们的电子结构进行了研究，结果表明它们是非常特殊的亚胺基钴配合物。计算分析证实了这些发现，并进一步揭示高自旋态是亚胺基特征的原因。用较小的均三甲苯基（2,4,6 - 三甲基苯基）取代亚胺上的Dipp取代基，导致意外的Me Si从辅助配体转移到亚胺基氮上，揭示了亚胺基单元具有高反应性的亲核特性。
