环金属化 (N,C) Au (III) 复合物:转变效应对它们的合成,结构和活性的影响
Marte Sofie Martinsen Holmsen1,2, Ainara Nova1,2,3,4, Mats Tilset1,2,3
1Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, N-0315 Oslo, Norway.
Accounts of chemical research
|December 5, 2023
概括
连接体的转效和转影响显著影响黄金的复杂化学,使得量身定制的复杂物体的设计成为可能. 了解这些效应对于控制黄金催化反应中的反应性至关重要.
科学领域:
- 有机金属化学 有机金属化学
- 黄金催化剂的使用方法
- 协调化学 协调化学
背景情况:
- 早期的黄金催化聚焦于Au (I) 和无机Au (III) 盐.
- 结合酶联体的开发使复杂的Au (III) 复合合成成为可能.
- 配体选择极大地影响了Au(III) 复合物的合成,特性和反应性.
研究的目的:
- 为了研究跨效应对环金属化 (N,C) Au (III) 复合物的影响.
- 阐明如何转化影响决定基化,阿里化和基化反应中的反应性.
- 了解跨效应在烯和乙烯功能化中的作用.
主要方法:
- 循环甲基酸盐 (N,C) Au(III) 复合物的合成和特征,特别是那些含有2-(p-tolyl) pyridine (tpy) 连接体的复合物.
- 分析反应结果 (化,化,化,化转化,/乙烯功能化) 基于连接物跨效应.
- 研究连接体替代和键断裂的动力学和热力学方面.
主要成果:
- 在tpy联体的终端 (tpy-C vs. tpy-N) 的跨影响决定了联体在 (tpy) Au(OAcF) 2复合体中的位置.
- 由于热力学偏好,诸如基功能化等反应主要发生在 trans 到 tpy-N 之间,而催化过程则有利于 trans 到 tpy-C.
- 在[(tpy) Au(π-allyl) ]+[NTf2]-中,乙烯三酸化和基联体协调显示出明显的区域选择性,受转变效应的支配.
结论:
- 转变效应对于控制Au (III) 复合物的反应性和选择性至关重要.
- 量身定制的 (N,C) Au (III) 综合体可以通过利用差异化的变压影响来设计.
- 了解跨效应对于推进黄金催化和有机金属合成至关重要.
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