组合DFT协议用于计算复合体中的PNMR转移
Svetlana A Kondrashova1, Shamil K Latypov1
1Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Kazan, Tatarstan 420088, Russian Federation. lsk@iopc.ru.
这项研究比较了复合物的计算和实验31P NMR转移. 理论计算通常与实验数据一致,根据的供体特性推特定的方法.
科学领域:
- 无机化学 无机化学
- 计算化学的计算化学
- 核磁共振光谱学 核磁共振光谱学
背景情况:
- 核磁共振 (NMR) 光谱对于表征化学结构至关重要.
- -31 (31P) 核磁共振对研究-复合体特别有用.
- 准确的NMR偏移理论预测有助于结构阐明.
研究的目的:
- 进行计算和实验31P NMR转移的比较分析.
- 评估不同理论方法的准确性,以预测复合体中的31P NMR转移.
- 根据捐赠体的特性,制定选择适当计算方法的指导方针.
主要方法:
- 计算和实验31P NMR数据的比较分析.
- 在完全相对论矩阵迪拉克-科恩-沙姆 (mDKS) 层面上利用了理论计算.
- 采用非相对论计算方法进行比较.
主要成果:
- 理论上的31P核磁共振转移通常对各种复合物 (Pt(0),Pt(II),Pt(IV)) 的实验数据复制得很好.
- 完全相对论的mDKS水平是必要的,以准确计算 σ-捐赠原子的 31P NMR 转移 (RMSE = 4.6 ppm).
- 非相对论方法可能足以 π-捐赠,但精度较低 (RMSE = 8.2 ppm).
结论:
- 这项研究为准确预测复合体中的31P NMR转移提供了一个框架.
- 方法的选择取决于联体的电子性质 (σ-捐赠者与π-捐赠).
- 这种方法促进了复杂结构的赋值,包括具有异构的结构.
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