National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577, Japan.
J Chem Phys. 2010 Feb 7;132(5):054504. doi: 10.1063/1.3299715.
Laser-ablated Ru and Rh atoms react with CO and N(2) mixture in excess neon to produce the carbonylmetal dinitrogen complexes, (NN)(n)MCO (M=Ru,Rh; n=1,2) and NNRu(CO)(2), as well as metal carbonyls and dinitrogen complexes. These carbonylmetal dinitrogen complexes are characterized using infrared spectroscopy on the basis of the results of the isotopic substitution and mixed isotopic splitting patterns. Density functional theory calculations have been performed on these complexes. Overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these species from the matrix infrared spectra. Furthermore, a plausible reaction pathway for the formation of the products has been proposed. This work reveals that the reactivity of Ru and Rh atoms toward CO is prior to N(2).
激光烧蚀的 Ru 和 Rh 原子与过量氖中的 CO 和 N(2)混合物反应，生成羰基金属二氮配合物(NN)(n)MCO（M=Ru，Rh；n=1,2）和 NNRu(CO)(2)，以及金属羰基和二氮配合物。这些羰基金属二氮配合物通过基于同位素取代和混合同位素分裂模式的红外光谱进行了表征。对这些配合物进行了密度泛函理论计算。实验和计算得到的振动频率、相对吸收强度和同位素位移之间的总体一致性支持从基质红外光谱中鉴定这些物质。此外，还提出了形成产物的可能反应途径。这项工作表明 Ru 和 Rh 原子对 CO 的反应活性优先于 N(2)。
