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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Matrix infrared spectroscopic studies of the MH-C2H3 and MH2-C2H2 intermediates in the reactions of ethylene with laser-ablated group 5 metal atoms
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Matrix infrared spectroscopic studies of the MH-C2H3 and MH2-C2H2 intermediates in the reactions of ethylene with laser-ablated group 5 metal atoms

机译：乙烯与激光烧蚀的5族金属原子反应中MH-C2H3和MH2-C2H2中间体的基质红外光谱研究

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摘要

Reactions of ethylene with laser-ablated group 5 metal atoms in excess argon have been carried out during codeposition at 8 K, and the matrix infrared spectra of intermediate products have been investigated. Oxidative C-H insertion of the transition metal into a C-H bond occurs and beta-hydrogen transfer follows to form the dihydrido complexes (MH2-C2H2). In the Ta spectra, the dihydrido complex is the primary product, whereas the Nb and V spectra reveal absorptions from both the insertion (MH-C2H3) and dihydrido complexes. The insertion and dihydrido complexes identified here are in fact the reaction intermediates in the hydrogen elimination of ethylene proposed in previous reaction dynamics studies. Calculations also show that the higher oxidation-state complex becomes more stable relative to the insertion product going down the group 5 family.
机译：在共沉积8 K的条件下，进行了乙烯与激光烧蚀的5族金属原子在过量氩气中的反应，并研究了中间产物的基质红外光谱。发生过渡金属到C-H键的氧化C-H插入，然后发生β-氢转移形成二氢配合物（MH2-C2H2）。在Ta光谱中，二氢配合物是主要产物，而Nb和V光谱显示了插入物（MH-C2H3）和二氢配合物的吸收。实际上，此处确定的插入和二氢配合物实际上是先前反应动力学研究中提出的乙烯脱氢反应的反应中间体。计算还表明，相对于第5组族的插入产物，较高的氧化态络合物变得更稳定。

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