Spectroscopic Study of Sol–Gel Entrapped Triruthenium Dodecacarbonyl Catalyst Reveals Hydride Formation
Spectroscopic Study of Sol–Gel Entrapped Triruthenium Dodecacarbonyl Catalyst Reveals Hydride Formation
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溶胶-凝胶包埋的十二羰基三钌催化剂的光谱研究揭示了氢化物的形成
DOI：
10.1021/acs.jpclett.0c02316
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Massari, Aaron M.
中科院分区：
文献类型：
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作者：
Patrow, Joel G.;Cheng, Yukun;Pyles, Cynthia G.;Luo, Bing;Tonks, Ian A.;Massari, Aaron M.
十二羰基三钌在氧化铝溶胶-凝胶中封装后，对氢化反应的催化活性增加。在本研究中，我们展示了由封装过程引起的结构和电子变化。傅里叶变换红外光谱（FTIR）表明，溶胶-凝胶玻璃在老化过程中羰基振动模式发生了显著的红移。这些变化归因于金属氢化物的形成：[HRu3(CO)11]−。与合成的[NEt4][HRu3(CO)11]的FTIR光谱比较证实了这一分配。XPS研究表明，[HRu3(CO)11]−的Ru 3d5/2峰也向结合能较低的方向移动，与Ru3(CO)12相比，Ru原子核上的电子密度增加相一致，密度泛函计算也证实了这一点。这项研究为进一步研究氢化物在先前观察到的催化活性中的作用打开了大门。据我们所知，这是第一个确定氧化铝溶胶-凝胶中存在[HRu3(CO)11]−的研究。
Triruthenium dodecacarbonyl exhibits increased catalytic activity toward hydrogenation reactions when encapsulated in alumina sol–gels. In this study, we demonstrate structural and electronic changes induced by the encapsulation process. Fourier transform infrared (FTIR) spectroscopy reveals that the carbonyl vibrational modes dramatically red shift during aging in the sol–gel glass. These shifts are attributed to the formation of the metal hydride: [HRu3(CO)11]−. A comparison to the FTIR spectrum of synthesized [NEt4][HRu3(CO)11] confirms this assignment. XPS studies show that the Ru 3d5/2peak of [HRu3(CO)11]−also shifts to lower binding energy, consistent with an increased electron density on the Ru nuclei compared to Ru3(CO)12and confirmed by density functional calculations. This study should open the door to further investigations into the hydride’s role in the previously observed catalytic activity. To the best of our knowledge, this is the first study to identify the presence of [HRu3(CO)11]−in the alumina sol–gel.