Inorganic Chemistry, University Erlangen-Nürnberg, 91058 Erlangen, Germany.
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
Science. 2021 Mar 12;371(6534):1125-1128. doi: 10.1126/science.abf2374.
Here we report that attempted preparation of low-valent Ca complexes in the form of LCa-CaL (where L is a bulky β-diketiminate ligand) under dinitrogen (N) atmosphere led to isolation of LCa(N)CaL, which was characterized crystallographically. The N - anion in this complex reacted in most cases as a very potent two-electron donor. Therefore, LCa(N)CaL acts as a synthon for the low-valent Ca complex LCa-CaL, which was the target of our studies. The N - anion could also be protonated to diazene (NH) that disproportionated to hydrazine and N The role of Ca d orbitals for N activation is discussed.
在这里，我们报告说，在氮气（N）气氛下尝试制备低价 Ca 配合物的形式 LCa-CaL（其中 L 是一个庞大的β-二酮腙配体）导致了 LCa（N）CaL 的分离，该配合物通过晶体学进行了表征。该配合物中的 N-阴离子在大多数情况下作为非常有效的双电子供体反应。因此，LCa（N）CaL 作为我们研究目标的低价 Ca 配合物 LCa-CaL 的合成子。N-阴离子也可以质子化形成二氮烯（NH），该二氮烯会歧化为肼和 N。讨论了 Ca d 轨道对 N 活化的作用。
