中性和阴离子伊米多基烯循环氨基碳 (CAAC) 复合物用于烯转化
Koushani Kundu1, Janis V Musso1, Mathis J Benedikter1
1Institute of Polymer Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany.
Chemistry (Weinheim an der Bergstrasse, Germany)
|June 27, 2023
概括
报告了新型胺基基烯循环氨基碳 (CAAC) 复合物的合成. 这些新的CAAC复合物在烯转化反应中表现出较高的活性,与N-异环碳类同类物相比.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 碳烯化学 碳烯化学
背景情况:
- 在催化过程中,像基烯复合物至关重要.
- 循环氨基碳酸 (CAACs) 是强大的西格玛捐赠体和pi接受体.
- N-异环碳 (NHCs) 是催化中常用的联体.
研究的目的:
- 为了合成和表征新的中性和阴离子 imido 基 CAAC 复合物.
- 研究这些新复合物的电子特性和催化活性.
- 为了比较它们的性能与类似的NHC复合物在olefin转化中的性能.
主要方法:
- 聚合莫利卜丁胺基基基基烯DME前体的合成.
- 使用单晶X射线分析进行表征.
- 计算研究 (PBE0-D3BJ/def2-TZVP) 用于分析电子属性.
- 在olefin转化反应中进行测试.
主要成果:
- 成功合成中性和阴离子Mo imido 基烯 CAAC 复合物.
- 在不需要额外的供体配体的情况下,CAAC配体提供稳定性.
- 计算显示,类似的电荷与NHC复合体相似,在CAAC复合体中极化较高.
- 阴离子CAAC复合体在碳化合物基质的烯转化中表现出更好的活性,在室温下达到高周转率 (TON).
- 一些复合物对功能组 (如硫和硫胺) 具有耐受性.
结论:
- 新型Mo imido基烯CAAC复合物为NHC类似物提供了一个有前途的替代品.
- 强大的供体/接受体特性提高了CAACs的催化性能.
- 这些复合物代表了催化烯转化酶的重大进步,特别是对于具有挑战性的基质.
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