从Sn (II) 到Sn (IV):通过氧化增强易斯酸度
Rini Prakash1, Jerin Joseph1, Alex P Andrews1
1School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Vithura Thiruvananthapuram 695551, Kerala, India.
Inorganic chemistry
|September 7, 2023
概括
我们表明, (IV) 化合物比 (II) 化合物更具有易斯酸性. 通过将化物替换为锡复合体中的三联体物来进一步增加易斯酸度.
科学领域:
- 有机金属化学 有机金属化学
- 易斯的酸度研究
- 锡化学 锡化学
背景情况:
- 易斯酸度是一种影响反应性的基本化学性质.
- 了解锡化合物的易斯酸度趋势对于催化是至关重要的.
- 连接体的电子和固体效应显著影响金属中心酸度.
研究的目的:
- 为了证明从Sn(II) 到Sn(IV) 氧化状态的易斯酸度增加.
- 为了研究连接体替代对锡的易斯酸度的影响.
- 为增强易斯酸度提供实验和计算证据.
主要方法:
- 锡复合物的合成和表征:TpMe2SnOTf,TpMe2SnF(OTf) 2,以及TpMe2Sn(OTf) 3.
- NMR光谱检测电子环境.
- 修改了古特曼 - 贝克特定位以量化易斯酸度.
- 计算分析 (例如,DFT) 来建模电子结构.
- 催化氧化物去氧化作为一个反应性探针.
主要成果:
- 从Sn (II) 到Sn (IV) 的氧化明显增加了易斯酸度.
- 在TpMe2SnF(OTf) 2中用triflate替换化物以形成TpMe2Sn(OTf) 3,进一步提高了易斯酸度.
- 包括光谱,定位,计算和催化在内的多种方法证实了观察到的酸度趋势.
结论:
- 与Sn (II) 相比,锡 (IV) 种的易斯酸度显著更高.
- 三甲酸对进一步增加Sn(IV) 复合体的易斯酸度是有效的.
- 合成的锡复合物作为有价值的易斯酸用于催化应用.
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