【摘要】 用原位红外光谱法研究了负载于MgO表面上的〔PPN〕₂〔Ru₃（CO）₉CCO〕簇合物。发现表面物类同MgO的抽空脱水温度有很大关系。在573K以下脱水的氧化镁上〔PPN〕₂〔Ru₃-（CO）₉CCO〕吸附后,其v_?=o的红外谱基本保持乙烯酮钌簇合物的原来特征,〔Ru₃（CO）₉-CCO〕^2-离子和表面的电荷相互作用只引起线式和桥式CO谱带的轻微位移。抽空脱水温度超过613K时,除了〔Ru₃（CO）₉CCO〕^2-的特征光谱外,还出现2068,2030和1999cm^-1新谱带,归因于Mg-OH同〔Ru₃（CO）₉CCO〕^2-反应部分地形成〔HRu₃（CO）₉CCO〕^-.TPD-IR研究揭示了〔Ru₃（CO）₉CCO〕^2-/MgO的热稳定性远大于〔PPN〕₂〔Ru₃（CO）₉CCO〕固体。在CO气氛下,〔Ru₃（CO）₉CCO〕^2-同CH₃I很易反应,v_?=o谱带的变化说明反应后有乙酰基生成,v_?=o谱带出现在1635cm^-1。这种含乙酰基的三钌化合物〔Ru₃（CO）₉CC（O）CH₃〕^-对CO+H₂合成C₂含氧物的机理研究,可能有模型化合物的意义。更多还原

【Abstract】 Infrared spectroscopio studies have been performed on the surface-bound [PPN]2[Ru3 (CO)BCCO] as a model compound for C2-oxygenates in CO hydro-genation. By the dehydration of MgO at 573K, the [PPN]2 (Ru3 (CO)9CCO] adsorbed on MgO exhibits the bands at 2024, 1979, 1951, 1898 and 1750 cm-1, which arc very close to the characteristic CO bands for the precursor dianion cluster. TPD study coupled with FT-IR revealed that the triruthenium ketenylidenc cluster on MgO is relatively much stable and the thermal decomposition temperature is raised up to near 473 K under vacuum. We therefore suggest that the dia- nion cluster is electrostatically interacted with the MgO surface dehydrated at a temperature below 573 K. By the strong dehydration of MgO at 673 K, in addition to the characteristic bands of [Ru3(CO)9CCO]2-, new bands appear at 2068, 2030 and 1999 cm-1 which are associated with those of [HRu3(CO)9-CCO]-. The formation of a hydride triruthenium species results from the surface reaction between acidic OH groups on MgO and[Ru3(CO)8CCO]2- species.Undet CO atmosphere, the species [Ru3(CO)9CCO]2- reacts with the CH3I to produce the acetyl cluster [RU3(CO)9CC(O)CH3]- as the intermediate model of C2-oxy-genales in CO hydrogenation. The acetyl cluster exhibits the carbonyl bands at 2022, 1980 and 1635 cm-1, and the C-H deformation stretching bands at 1462 and 1350 cm-1.更多还原