Hydrido-Ruthenium Cluster Complexes as Models for Reactive Surface Hydrogen Species of Ruthenium Nanoparticles. Solid-State 2H NMR and Quantum Chemical Calculations
Hydrido-Ruthenium Cluster Complexes as Models for Reactive Surface Hydrogen Species of Ruthenium Nanoparticles. Solid-State 2H NMR and Quantum Chemical Calculations
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DOI：
10.1021/ja104229a
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发表时间：
2010-08-25
影响因子：
15
通讯作者：
Buntkowsky, Gerd
中科院分区：
文献类型：
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作者：
Gutmann, Torsten;Walaszek, Bernadeta;Buntkowsky, Gerd
氢-2四极相互作用是表征氢-金属结合态的一种灵敏工具。在本研究中，实验固态H-2MAS核磁共振技术被用来研究两个Ru簇合物，D4Ru4(CO)(12)(1)和D2Ru6(CO)(18)(2)，它们是金属表面典型的两重、三重和八面体配位的模型化合物。通过对样品1的H-2MAS核磁共振线形分析，得到四极耦合常数为67+/-1 kHz，不对称参数为0.67+/-0.1，各向同性化学位移为-17.4ppm。除中性络合物外，样品2还包括两个离子簇，分别为阴离子[DRu6(CO)(18)](-)(2(-))和阳离子[D3Ru6(CO)(18)](+)(2(+))。由于极弱的四极相互作用(
The H-2 quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state H-2 MAS NMR techniques are used in the investigations of two ruthenium clusters, D4Ru4(CO)(12) (1) and D2Ru6(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the H-2 MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic [DRu6(CO)(18)](-) (2(-)) and cationic [D3Ru6(CO)(18)](+) (2(+)). By virtue of the very weak quadrupolar interaction (