Dinitrogen complexation and reduction at low-valent calcium
Dinitrogen complexation and reduction at low-valent calcium
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DOI：
10.1126/science.abf2374
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发表时间：
2021-03-12
期刊：
影响因子：
56.9
通讯作者：
Harder, S.
中科院分区：
文献类型：
--
作者：
Roesch, B.;Gentner, T. X.;Harder, S.
在这里，我们报告，试图在二氮（N-2）气氛下制备LCa-CaL（其中L是一个庞大的β-双烯酮亚胺配体）形式的低价钙-I络合物导致LCa（N-2）CaL的分离，其特征在于晶体学。该配合物中的N-2（2-）阴离子在大多数情况下作为一个非常有效的双电子供体反应。因此，LCa（N-2）CaL作为低价Ca-I复合物LCa-CaL的合成子，这是我们研究的目标。N-2（2-）阴离子也可以质子化为二氮烯（N2 H2），二氮烯（N2 H2）再质子化为肼和N-2。讨论了Ca d轨道对N-2活化的作用。
Here we report that attempted preparation of low-valent Ca-I complexes in the form of LCa-CaL (where L is a bulky beta-diketiminate ligand) under dinitrogen (N-2) atmosphere led to isolation of LCa(N-2)CaL, which was characterized crystallographically. The N-2(2-) anion in this complex reacted in most cases as a very potent two-electron donor. Therefore, LCa(N-2)CaL acts as a synthon for the low-valent Ca-I complex LCa-CaL, which was the target of our studies. The N-2(2-) anion could also be protonated to diazene ( N2H2) that disproportionated to hydrazine and N-2. The role of Ca d orbitals for N-2 activation is discussed.