Umpolung of electrophilic terminal phosphinidene complexes: coordination chemistry to phosphorus and gateway to the chemistry of low-coordinate P-based super-electrophiles

亲电子末端膦配合物的反极性：磷的配位化学和低配位P基超亲电子试剂化学的大门

• 批准号: 404441187
• 负责人: Professor Dr. Rainer Streubel
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/404441187?language=en
• 关键词: Umpolung; electrophilic; terminal; phosphinidene; complexes

Major aim of the research project is to develop new methodologies to generate novel, highly electrophilic low valent phosphorus species, able to activate small molecules. Starting point for the study should be end-on donor-stabilized terminal, electrophilic phosphinidene complexes (EPCs), i.e. "umgepolte" EPCs. Their structure/reactivity relationship shall be studied, focusing on the following processes at the phosphorus centre: oxidation/oxidative addition (A) and protonation (B). In part A we will study oxidation reactions of end-on donor EPC adducts in order to synthesize highly electrophilic phosphinidene-oxide complexes (EPOCs), but also pathways of oxidative addition reactions of species having differently polarized polar E-E’ bonds. In part B we will react end-on donor EPC adducts with strong Brønsted acids (i) or 1,1’-bifunctional chlorophosphane complexes with chloride abstractors (ii). This should open the gateway to novel protonated EPCs (PEPCs), and important for their reactivity is that reactants in i) and ii) possess weakly coordinating anions (WCAs). Such PEPCs will be examined in small molecule activation such as CO2, N2 and P4. In total, the project should not only lead to new fundamental insights into the coordination/ organometallic chemistry of the non-metal element phosphorus, but also create new mild, powerful synthetic methods. Theoretical studies will be performed in close collaboration with A. Espinosa (Spain).

该研究项目的主要目的是开发新的方法来产生新的，高度亲电的低价磷物种，能够激活小分子。研究的起点应该是端对端供体稳定的末端亲电膦烯复合物（EPC），即“umgepolte”EPC。应研究其结构/反应性关系，重点关注磷中心的以下过程：氧化/氧化加成（A）和质子化（B）。在A部分中，我们将研究末端供体EPC加合物的氧化反应，以合成高度亲电的膦酰氧化物复合物（EPOC），以及具有不同极化极性E-E'键的物质的氧化加成反应的途径。在部分B中，我们将使末端供体EPC加合物与强布朗斯特酸（i）或1，1 '-双官能氯膦络合物与氯化物提取剂（ii）反应。这将打开通向新型质子化EPC（PEPC）的大门，并且对于它们的反应性而言重要的是i）和ii）中的反应物具有弱配位阴离子（WCA）。将在小分子活化如CO2、N2和P4中检查此类PEPC。总的来说，该项目不仅应该导致对非金属元素磷的配位/有机金属化学的新的基本见解，而且还应该创造新的温和，强大的合成方法。理论研究将与A.埃斯皮诺萨（西班牙）。