Dinitrogen fixation with low-valent iron and cobalt complexes bearing phosphinidenides

含磷酰亚胺的低价铁和钴络合物的二氮固定

• 批准号: 465032298
• 负责人: Dr. Luong Phong Ho
• 金额: --
• 依托单位: Shanghai Institute of Organic Chemistry
• 依托单位国家: 德国
• 项目类别: WBP Fellowship
• 财政年份: 2021
• 资助国家: 德国
• 起止时间: 2020-12-31 至 无数据
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/465032298?language=en
• 关键词: Dinitrogen; fixation; low; valent; iron

The general strategy for this project involves the use of NHC/CAAC-phosphinidenes and NHC/CAAC-phosphinidenidesfor the synthesis of iron and cobalt complexes and the subsequent examination of their abilities to fixate dinitrogen under reductive conditions. By merging the expertise of the applicant in NHC-main group element chemistry with the experience of the host institution in iron- and cobalt-chemistry, the isolation of several novel complexes are envisaged. Especially the N2 activation with di- or- tri-nuclear complexes can be regarded as the main target of this investigation.Despite the recent popularity of NHC-phosphinidenes and NHC-phosphinidenides, only few corresponding iron or cobalt complexes were established. Furthermore, the fact that many dinitrogen-iron and -cobalt complexes rely on phosphane based ligands, the investigation of such phosphinidene or phosphinidenide based complexes regarding the change of activity is certainly of interest. In analogy to the (NHC)P– ligand, related CAAC ligands can also be used, since (CAAC)P– ligands in transition metal complexes are not reported yet. The work program is formulated along the following objectives:-Synthesis and characterization of NHC/CAAC-phosphinidenes as ligands as well as transfer reagents for the NHC/CAAC-phosphinidenide moieties-Synthesis and characterization of low valent iron- and cobalt-complexes bearing NHC/CAAC-phosphinidene and -phosphinidenide ligands-Investigation of these complexes regarding dinitrogen fixation and dinitrogen activation under reductive conditions-Investigation of the potential dinitrogen complexes regarding ammonia and N–C/Si bond formation

该项目的总体策略涉及使用NHC/CAAC-次膦酰亚胺和NHC/CAAC-次膦酰亚胺来合成铁和钴络合物，并通过合并申请人的专业知识来检查它们在还原条件下固定二氮的能力。 NHC-主族元素化学结合主办机构在铁和钴化学方面的经验，设想分离几种新型配合物，特别是N2。尽管NHC-次膦酰亚胺和NHC-次膦酰亚胺化合物的活化可以被视为本研究的主要目标，但仅建立了很少的相应的铁或钴络合物。二氮-铁和-钴配合物依赖于膦基配体，对此类膦亚胺或膦亚胺基配合物的研究涉及与(NHC)P-配体类似，也可以使用相关的CAAC配体，因为过渡金属配合物中的(CAAC)P-配体尚未被报道。目标如下：-作为 NHC/CAAC-次膦酰基配体以及 NHC/CAAC-次膦酰基部分的转移试剂的合成和表征-低带有NHC/CAAC-次膦酰亚胺和-次膦酰亚胺配体的价铁和钴配合物-研究这些配合物在还原条件下的二氮固定和二氮活化作用-研究有关氨和N-C/Si键形成的潜在二氮配合物