通过Organoantimony ((V) Pnictogen Bond Donors进行阳离子结合位的无菌选择:一个实验和计算研究
Brendan L Murphy1, Logan T Maltz1, François P Gabbaï1
1Department of Chemistry, Texas A&M University, College Station, Texas 77843-3255, United States.
Inorganic chemistry
|December 3, 2024
概括
三甲基酸提博具有不同的易斯酸度和化物结合偏好. 固态阻碍影响酸度,而电子因素和σ孔则决定这些化合物中的离子结合几何.
科学领域:
- 有机金属化学 有机金属化学
- 易斯酸催化剂的使用
- 计算化学计算化学
背景情况:
- катехолатостиборан因其作为易斯酸的功用而越来越受认可.
- 了解这些化合物的结构-性质关系对于优化它们的应用至关重要.
研究的目的:
- 为了研究两个三甲基酸的易斯酸度, (o-C6Cl4O2) Sb (o-Tol) 3和 (o-C6Cl4O2) Sb (p-Tol) 3.3.
- 为了阐明控制它们的离子结合偏好和几何学的因素.
主要方法:
- 化物离子结合研究是为了评估易斯酸度进行的.
- 计算分析,包括激活应变分析,用于检查电子结构和粘合.
- 整形和副托利替代物的固体和电子效应的比较.
主要成果:
- 帕拉-托利基衍生物 (3) 显示出比正极-托利基衍生物 (2) 更大的易斯酸度.
- 在 (2) 中的反中心周围的绝缘拥挤被确定为影响其降低的易斯酸度的关键因素.
- 化合物 (3) 将化物转化物与Sb-C键结合,而 (2) 则更喜欢将转化物结合与Sb-O键结合.
- 计算分析揭示了 σ 孔的存在,并解释了观察到的离子结合几何.
结论:
- 易斯酸度在triarylcatecholatostiboranes是敏感的,以 steric 作用的aryl替代品.
- 阳离子结合几何学受到电子因素,σ孔相互作用和硬质考虑因素的组合的影响.
- 这些发现为设计和应用新的易斯酸性stiboranes提供了洞察力.
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