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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Infrared spectra of M-η2-C2H2 and HM-C≡CH produced in reactions of laser-ablated group 6 metal atoms with acetylene
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Infrared spectra of M-η2-C2H2 and HM-C≡CH produced in reactions of laser-ablated group 6 metal atoms with acetylene

机译：激光烧蚀的6族金属原子与乙炔反应生成的M-η2-C2H2和HM-C≡CH的红外光谱

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摘要

The π and C-H insertion complexes (M-η2-C 2H2 and HM-C≡CH) are identified in the matrix infrared spectra from reactions of laser-ablated Group 6 metal atoms with acetylene. In annealing, the π complex is produced, and it converts to the insertion product during photolysis with no trace of the vinylidene product. This observation is consistent with the considerably higher activation energy to H2CCM than that to HM-CCH in the previously proposed reaction path, whereas the three plausible products are in fact energetically comparable. The back-donations in the Group 6 metal π complexes are evidently weaker than those in the Groups 3-5 metal analogues but still stronger than those in the main group and Group 7-10 metal systems. The insertion complexes have bent CMH moieties in contrast with the linear Mn complex.
机译：通过激光烧蚀的6族金属原子与乙炔的反应，在基质红外光谱中鉴定出π和C-H插入配合物（M-η2-C2H2和HM-C≡CH）。在退火过程中，会生成π络合物，并且在光解过程中会转化为插入产物，而没有痕量的亚乙烯基产物。该观察结果与在先前提出的反应路径中对H 2 CCM的活化能明显高于对HM-CCH的活化能一致，而实际上这三种可能的产物在能量上是可比的。第6组金属π络合物的回馈作用明显弱于第3-5组金属类似物，但仍强于主要组和第7-10组金属体系。与线性Mn配合物相比，插入配合物具有弯曲的CMH部分。

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