Design and preparation of dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand and their application to catalytic dinitogen fixation

以二氮桥联的双钼络合物和PNP型钳形配体为催化剂，建立了一种将分子氮直接转化为氨的新催化体系。因此，使用含砷的ANA型钳形配体中的膦取代Ars是本研究的重点，因为Ars与膦具有相似的配位方式，但也被认为比膦更不愿氧化，空间更大，S给体和p-受体比膦更差。合成了新型的含砷ANA型钳形配体的单钼氮配合物，并通过X-射线分析对其进行了表征。通过在室温下用硫酸处理，这些络合物提供了化学计量的氨。

A new catalytic system to convert molecular dinitrogen directly into ammonia has been achieved using a dinitrogen-bridged dimolybdenum complex with a PNP-type pincer ligand as a catalyst. Thus the use of an arsenic-containing ANA-type pincer ligand where phosphines in the PNP-type pincer ligand are substituted for arsines has been focuse on in this reserch, for arsines are known to have similar coordination modes to phosphines, but are also recognized to be more reluctant to oxidation, sterically bulkier, and poorer s-donors and p-acceptors compared to phosphines.Novel mono- and dimolybdenum-dinitrogen complexes bearing an arsenic-containing ANA-type pincer ligand are prepared and characterized by X-ray analyses. These complexes afford a stoichiometric amount of ammonia by treatment with sulfuric acid at room temperature.