Aghazada Sadig, Fehn Dominik, Heinemann Frank W, Munz Dominik, Meyer Karsten
Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Inorganic Chemistry, Egerlandstrasse 1, 91058, Erlangen, Germany.
Current address: Saarland University, Inorganic Chemistry: Coordination Chemistry, Campus 4.1, 66123, Saarbrücken, Germany.
Angew Chem Int Ed Engl. 2021 May 10;60(20):11138-11142. doi: 10.1002/anie.202016539. Epub 2021 Apr 8.
Lithium trimethylsilyldiazomethanide and a cobalt (II) precursor with an N-anchored tris-NHC (TIMEN ) ligand provide access to the cobalt nitrilimide 1. Complex 1 was structurally characterized by single-crystal X-ray diffractometry (SC-XRD) and its electronic structure was examined in detail, including EPR spectroscopy, SQUID magnetometry and computational analyses. The desilylation of the C-(trimethylsilyl)nitrilimide reveals a transient complex with an elusive diazomethanediide ligand, which substitutes one of the mesitylene rings of the ancillary ligand through C-N bond cleavage. This transformation results in the cyclometalated cobalt(II) complex 2, featuring a rare isocyanoamido-κ-C ligand.
三甲基硅基重氮甲烷锂与一种带有N-锚定三氮杂环卡宾（TIMEN）配体的钴（II）前体可用于制备钴氮酰亚胺1。配合物1通过单晶X射线衍射法（SC-XRD）进行了结构表征，并对其电子结构进行了详细研究，包括电子顺磁共振光谱、超导量子干涉仪磁力测量和计算分析。C-（三甲基硅基）氮酰亚胺的去硅基化反应揭示了一种带有难以捉摸的重氮甲烷二价阴离子配体的瞬态配合物，该配体通过C-N键断裂取代了辅助配体的一个均三甲苯环。这种转化产生了环金属化钴（II）配合物2，其具有罕见的异氰基酰胺-κ-C配体。
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