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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Matrix Infrared Spectra of the C—H Insertion and Dihydrido Cyclic Products from Reactions of Group 3 Metal Atoms with Ethylene
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Matrix Infrared Spectra of the C—H Insertion and Dihydrido Cyclic Products from Reactions of Group 3 Metal Atoms with Ethylene

机译：3族金属原子与乙烯反应的CH插入和二氢环状产物的基体红外光谱

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摘要

Reactions of laser-ablated Group 3 metal atoms with ethylene isotopomers have been carried out, and the primary products have been identified in the matrix IR spectra. The insertion and dihydrido cyclic products (HM—C_2H_3 and H_2M—C_2H_2) are identified from the matrix IR spectra of Sc and Y, whereas only the insertion product is observed in the La spectra along with many lanthanium hydride absorptions. The observed metal hydride absorptions suggest that the H_2-elimination reaction becomes faster upon going down the group column, and the trend is also consistent with the energies of the H_2-elimination products relative to those of the dihydrido cyclic products. The present results support the conclusion that C—H insertion and following H migration from C to M are in fact general phenomena in reactions of early transition metals (Groups 3-6) and actinides with ethylene. The back-donation of electron-deficient Group 3 metals to the 7r-cyclic system of H_2M—C_2H_2 is evidently much weaker than that of the previously studied systems.
机译：已经进行了激光烧蚀的第3组金属原子与乙烯同位异构体的反应，并且在基体红外光谱中鉴定出主要产物。从Sc和Y的基体红外光谱中识别出插入和二氢环状产物（HM-C_2H_3和H_2M-C_2H_2），而在La光谱中仅观察到插入产物以及许多氢化镧吸收。观察到的金属氢化物吸收表明，H 2消除反应在下降到基团柱后变得更快，并且该趋势也与H_2消除产物的能量相对于二氢环状产物的能量一致。本结果支持这样的结论，即CH插入以及H从C迁移至M后实际上是早期过渡金属（3-6族）和act系元素与乙烯反应的普遍现象。缺电子的3族金属向H_2M-C_2H_2的7r循环系统的背向供电明显弱于先前研究的系统。

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