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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-η~2-C_2H_2, HM-C≡CH, and HM-C≡CH- Prepared in reactions of Laser-Ablated group 3 metal atoms with acetylene
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Infrared spectra of M-η~2-C_2H_2, HM-C≡CH, and HM-C≡CH- Prepared in reactions of Laser-Ablated group 3 metal atoms with acetylene

机译：激光烧蚀3族金属原子与乙炔反应制备的M-η〜2-C_2H_2，HM-C≡CH和HM-C≡CH-的红外光谱

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摘要

The major HM-C≡CH and M-η~2-C_2H_2 products are observed in the matrix infrared spectra from reactions of laser-ablated group 3 metal atoms with acetylene, while the vinylidene product is not detected. These results reveal that coordination of group 3 metal atoms to the acetylene π-bond and H-migration from C to M readily occur during codeposition and photolysis afterward. The product absorption assigned to the La-vinylidene complex in a previous study is reassigned to one of the absorptions of La-η~2-C_2H_2?C_2H_2. Two strong Sc-H stretching absorptions are assigned to the free HSc-CCH~- anion, in accord with a previous study, but a lower frequency counterpart is reassigned to HSc-CCH~- coordinated to acetylene based on the increasing relative intensity of the low-frequency component at higher acetylene concentration. The group 3 metals evidently form weaker π-complexes than the group 4 metals. The addition of an electron to HM-CCH elongates the M-H and M-C bonds in the anionic species due to the lower ionic contributions to the bonding.
机译：在激光烧蚀的3族金属原子与乙炔的反应中，在基质红外光谱中观察到主要的HM-C≡CH和M-η〜2-C_2H_2产物，而未检测到亚乙烯基产物。这些结果表明，在共沉积和随后的光解过程中，容易发生3族金属原子与乙炔π键的配位以及H从C迁移到M。在先前的研究中，分配给La-亚乙烯基配合物的产物吸收被重新分配为La-η〜2-C_2H_2→C_2H_2的吸收之一。根据先前的研究，两个强的Sc-H拉伸吸收被分配给游离的HSc-CCH〜-阴离子，但是，基于较低的相对强度的增加，低频的对应物被重新分配给HSc-CCH〜-与乙炔配位。乙炔浓度较高时的低频分量。第3族金属显然比第4族金属形成更弱的π-络合物。由于较低的离子对键合的贡献，因此向HM-CCH添加电子可延长阴离子物种中的M-H和M-C键。

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