在Rh2S2核心的双核复合体上激活分子:DFT计算和NMR机理学研究
Andrea Ienco1, Maria José Calhorda, Joachim Reinhold
1Istituto di Chimica dei Composti OrganoMetallici, CNR, Via Madonna del Piano, I-50019 Sesto Fiorentino, Firenze, Italy.
这项研究研究了激活二的-硫复合体. DFT计算和NMR实验揭示了一个单化物-mu-硫化物中间体,澄清了二激活的反应途径.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 计算化学计算化学
背景情况:
- 已知二三复合体可以激活二.
- 一个二复合物与其 bis ((mu-hydrosulfido) 产物之间的可逆转化涉及二激活.
- 了解这种二激活的机械路径对于催化剂设计至关重要.
研究的目的:
- 通过使用DFT计算,研究使用二三复合物的二激活所涉及的可能步骤.
- 用 (31) P和 (1) H NMR光谱学,包括对技术,实验性地确定实际反应途径.
- 阐明中间体在可逆二激活过程中的作用.
主要方法:
- 密度函数理论 (DFT) 计算以建模反应机制和能量障碍.
- (31) P和 (1) H核磁共振 (NMR) 光谱法用于识别反应中间体.
- 在NMR实验中使用了Para-技术来探测反应路径.
主要成果:
- DFT计算表明二激活和分裂的两个潜在途径.
- 实验 (1) H NMR 数据确定了单个反应中间体,即单化物--硫化物复合物.
- 没有发现过渡的Rh-{eta}{2) -H{2)) adduct的实验证据,可能是由于其寿命短.
结论:
- 实验结果排除了其中一个假设的途径,证实了单化物--硫化物中间体的形成.
- 计算能量配置文件支持整体二激活和可逆过程的可行性.
- 对于H(2) 激活的最高能量障碍是8.6 kcal mol(-1),对于可逆过程,观察到34.6 kcal mol(-1的可克服障碍.
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