Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA.
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, Germany.
Nat Chem. 2022 Aug;14(8):928-934. doi: 10.1038/s41557-022-00958-5. Epub 2022 Jun 13.
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≡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 °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 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.
氮化磷（PN）在地球上仅短暂存在，因此在温和条件下，用于在溶液中释放这种分子的分子前体仍然难以捉摸。在这里，我们报告了一种基于蒽的前体的合成，该前体具有穿过其中环的叠氮膦桥，在溶液中以大约 30 分钟的一级半衰期分解为二氮，蒽和 P≡N，在室温下。在减压下加热时，如分子束质谱研究所示，这种叠氮膦-蒽前体以爆炸的方式在大约 42°C 下分解。该前体还被证明可以作为 PN 转移试剂，通过与 Fe-N 对应物的配体交换，用于合成 Fe-NP 配位配合物。与 P 键合的异构体相比，由于显著的共价 Fe-杂原子键特征和相关的金属-配体相互作用中较小的不利的 Pauli 排斥，末端 N 键合的配合物在能量上是优选的。
