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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mechanism of Acetylene-Vinylidene Rearrangement with Na, Al, and Y Atoms
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Mechanism of Acetylene-Vinylidene Rearrangement with Na, Al, and Y Atoms

机译：Na，Al和Y原子进行乙炔-亚乙烯基重排的机理

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摘要

Reaction pathways are identified for Na-, Al-, and Y-induced acetylene (HCCH)-vinylidene (CCH_2) rearrangements in the gas phase. Density functional and coupled cluster calculations are performed with basis set extrapolations. The rearrangement barriers decrease from 44.0 kcal/mol in the metal-free reaction to 41.3 (Na), 19.1 (Al), and 16.1 (Y) kcal/mol in the metal-induced reactions. This decrease results from the strengthening of the M-C bonds (Na-C < Al-C < Y-C) in the M(HCCH) and M(CCH_2) complexes. Natural bond oribital analysis reveals the metallacyclopropene and metallaallene character of several of the M(HCCH) and M(CCH_2) complexes. In addition, analysis of the transition states provides a detailed picture of the redistribution of bonding and nonbonding electrons along the reaction pathway. The metal-free and Na-induced rearrangements proceed via 1,2-hydride shifts, whereas the Al- and Y-induced reactions proceed via 1,2-hydrogen shifts. The latter reactions involve homolytic bond cleavage and formation, with the α and β electron densities undergoing redistribution in opposing directions.
机译：确定了气相中Na-，Al-和Y诱导的乙炔（HCCH）-亚乙烯基（CCH_2）重排的反应途径。密度泛函和耦合聚类计算通过基集外推进行。重排势垒从无金属反应中的44.0 kcal / mol降至金属诱导反应中的41.3（Na），19.1（Al）和16.1（Y）kcal / mol。这种减少是由于M（HCCH）和M（CCH_2）配合物中M-C键的增强（Na-C

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