Taming phosphorus mononitride
Taming phosphorus mononitride
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DOI：
10.1038/s41557-022-00958-5
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发表时间：
2022-06-13
期刊：
影响因子：
21.8
通讯作者：
Cummins, Christopher C.
中科院分区：
文献类型：
--
作者：
Eckhardt, Andre K.;Riu, Martin-Louis Y.;Cummins, Christopher C.
一氮化磷（PN）在地球上只存在一瞬间，在温和的溶液条件下释放这种分子的分子前体仍然难以捉摸。在这里，我们报告的蒽为基础的catalysor-an蒽部分具有一个叠氮膦桥在其中心环，分解成二氮，蒽和P相当于N在溶液中的一阶半衰期约为30分钟，在室温下的合成。在减压下加热，这种叠氮膦-蒽前体在42摄氏度左右以爆炸方式分解，正如分子束质谱研究所证明的那样。该前体也被证明是作为PN转移试剂的Fe-NP配位络合物的合成，通过与其Fe-N-2对应的配体交换。末端N-键合的复合物被认为是积极的首选，相比其P-键合的连接异构体，由于一个显着的共价Fe-氮族元素键的字符和相关的不利泡利排斥在金属-配体相互作用。
Phosphorus mononitride (PN) only has a fleeting existence on Earth, and molecular precursors for the release of this molecule under mild conditions in solution have remained elusive. Here we report the synthesis of an anthracene-based precursor-an anthracene moiety featuring an azidophosphine bridge across its central ring-that dissociates into dinitrogen, anthracene and P equivalent to N in solution with a first-order half-life of roughly 30 min at room temperature. Heated under reduced pressure, this azidophosphine-anthracene precursor decomposes in an explosive fashion at around 42 degrees C, as demonstrated in a molecular-beam mass spectrometry study. The precursor is also shown to serve as a PN transfer reagent in the synthesis of an Fe-NP coordination complex, through ligand exchange with its Fe-N-2 counterpart. The terminal N-bonded complex was found to be energetically preferred, compared to its P-bonded linkage isomer, owing to a significant covalent Fe-pnictogen bond character and an associated less unfavourable Pauli repulsion in the metal-ligand interaction.