在基-维尼利丁重组过程中,凝结芳香碳化合物的迁移
Marcus Korb1, Seyed M B H Ghazvini1, Paul J Low1
1School of Molecular Sciences, The University of Western Australia, 35 Stirling Highway, Crawley, Western Australia, 6009, Australia.
在二甲基乙烯上存在较大的芳香基,有助于金属复合体中维尼利丁联结体的形成. 固态因素,包括分子体积和限制访问,影响反应效率和产品产量.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
背景情况:
- 含有凝聚的芳香碳化合物碎片的二甲基乙烯是有价值的前体.
- 乙烯联体在有机金属化学中至关重要.
研究的目的:
- 为了研究半三明治复合体内的1,2-diarylacetylenes的迁移.
- 了解硬质因子在维尼利丁连接体形成中的作用.
主要方法:
- 使用[MII(dppe) Cp]+复合体 (MII = RuII,FeII) 来合成来自二甲基乙烯的维尼利丁联体.
- 对不同基群大小的反应范围进行比较分析.
主要成果:
- 较大的分子体积和缓解硬质拥堵促进了维尼利丁的形成.
- 基H原子的接近限制了基的访问,降低了迁移效率.
- 对1-基实体观察到易于迁移,而1,2-bis(9-基) 乙烯的产量较低.
结论:
- 绝缘因素,包括分子体积和限制访问,显著影响二甲乙烯到利丁联体的转化.
- 竞争的固体效应决定了1,2-迁移反应的有效性.
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