稳定NH-组与裸相邻的稳定性 (II) 基中稳定氨基烯基中的原子
Madhusudan K Pandey1, Zohreh Hendi1, Xiaobai Wang1
1Institut für Anorganische Chemie, Georg-August-Universität Göttingen, 37077, Göttingen, Germany.
Angewandte Chemie (International ed. in English)
|December 22, 2023
概括
这项研究报告了第一个基稳定的自由氨基烯,这些化合物具有相邻的活性NH和Si (II) 位点. 这些新型氨基烯表现出明显的反应性,包括分子内C-H激活和1,2-转移,并且可以与金属中心协调.
科学领域:
- 有机化学 有机化学
- 主群 化学 化学
- 协调化学 协调化学
背景情况:
- 氨基烯,具有相邻的NH和Si (II) 部分,具有高度反应性,难以稳定.
- 以前的努力没有成功地分离出能容忍与裸体Si (II) 原子一起反应性NH组的氨基烯.
研究的目的:
- 合成和描述第一个基稳定自由氨基烯的例子.
- 为了研究这些稳定型氨基烯的独特反应模式.
- 探索氨基烯与过渡金属前体的协调行为.
主要方法:
- 新型基稳定氨基烯Ar*NHSi(PhC(NtBu) 2) 和Mes*NHSi(PhC(NtBu) 2) 的合成.
- 热反应性研究包括分子内C(sp3)-H激活和1,2-转移.
- 使用Ru(II) 和Fe(0) 前体进行协调研究,随后对产生的复合物进行表征.
- 密度函数理论 (DFT) 计算以阐明结构性,粘合性和能量性质.
主要成果:
- 成功分离了两个基稳定的自由氨基烯,Ar*NHSi(PhC(NtBu)2) (1a) 和Mes*NHSi(PhC(NtBu)2) (1b).
- 氨基1a经过了分子内C(sp3)-H激活,形成了一个循环.
- 阿米诺西1b表现出一种罕见的1,2-转移,产生了一种西兰胺.
- 氨基1a与Ru(II) 和Fe(0) 前体的复合导致了新的有机金属复合物.
结论:
- 基础稳定的自由氨基烯的开发克服了以前的稳定挑战.
- 这些化合物表现出多样化和独特的反应性,提供新的合成途径.
- 该研究扩大了氨基烯化学的范围及其在协调化学中的实用性.
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