Reactivity of molybdenum-nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles
Reactivity of molybdenum-nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles
复制标题
DOI：
10.1039/d1dt03952k
复制
发表时间：
2021-12-22
影响因子：
4
通讯作者：
Nishibayashi, Yoshiaki
中科院分区：
文献类型：
--
作者：
Itabashi, Takayuki;Arashiba, Kazuya;Nishibayashi, Yoshiaki
带有衍生自二氮的基于吡啶的PNP型钳配体的钼-氮化物络合物与各种以碳为中心的亲电子试剂反应，以使钼络合物中的氮化物配体官能化。氮化物络合物用 MeOTf 甲基化并用二苯乙酰氯酰化，通过碳-氮键形成提供相应的酰亚胺络合物。在与异氰酸苯酯和二苯基乙烯酮反应的情况下，PNP配体作为非无害配体分别形成相应的脲酸酯和酰亚胺络合物。这些新合成的复合物通过 X 射线分析进行表征。作为所制备的酰亚胺络合物的进一步转化，钼-酰亚胺络合物进行水解，得到作为有机氮化合物的相应酰胺以及相应的钼-氧络合物。该结果表明氮分子在氮化钼络合物的介导下转化为有机酰胺。
A molybdenum-nitride complex bearing a pyridine-based PNP-type pincer ligand derived from dinitrogen is reacted with various kinds of carbon-centered electrophiles to functionalize the nitride ligand in the molybdenum complex. Methylation with MeOTf and acylation with diphenylacetyl chloride of the nitride complex afford the corresponding imide complexes via a carbon-nitrogen bond formation. In the case of reactions with phenylisocyanate and diphenylketene, the PNP ligand works as a non-innocent ligand to form the corresponding ureate and acylimide complexes, respectively. These newly synthesized complexes are characterized by X-ray analysis. As a further transformation of the prepared imide complexes, hydrolysis of the molybdenum-acylimide complex proceeds to give the corresponding amide as an organonitrogen compound together with the corresponding molybdenum-oxo complex. This result indicates that the nitrogen molecule is converted into organic amide mediated by the molybdenum-nitride complex.