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Bastiaan Kooij Zhaowen Dong Farzaneh Fadaei-Tirani Rosario Scopelliti Kay Severin 《Angewandte Chemie (International ed. in English)》2023,62(34):e202308625
Bent (hetero)allenes such as carbodicarbenes and carbodiphosphoranes can act as neutral C-donor ligands, and diverse applications in coordination chemistry have been reported. N-Heterocyclic diazoolefins are heterocumulenes, which can function in a similar fashion as L-type ligands. Herein, we describe the synthesis and the reactivity of an anionic diazoolefin. This compound displays distinct reactivity compared to neutral diazoolefins, as evidenced by the preparation of diazo compounds via protonation, alkylation, or silylation. The anionic diazoolefin can be employed as an ambidentate, X-type ligand in salt metathesis reactions with metal halide complexes. Extrusion of dinitrogen was observed in a reaction with PCl(NiPr2)2, resulting in a stable phosphinocarbene. 相似文献
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Paul Varava Tak Hin Wong Zhaowen Dong Anastasia Yu. Gitlina Andrzej Sienkiewicz Wolfram Feuerstein Rosario Scopelliti Farzaneh Fadaei-Tirani Kay Severin 《Angewandte Chemie (International ed. in English)》2023,62(25):e202303375
The head-to-tail dimerization of N-heterocyclic diazoolefins is described. The products of these formal (3+3) cycloaddition reactions are strongly reducing quinoidal tetrazines. Oxidation of the tetrazines occurs in a stepwise fashion, and we were able to isolate a stable radical cation and diamagnetic dications. The latter are also accessible by oxidative dimerization of diazoolefins. 相似文献
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