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首页> 外文期刊>Journal of mass spectrometry: JMS >Reaction pathways of Sc~+ (~3D, ~1D) and Fe+ (~6D, ~4F) with acetone in the gas phase: Metal ion oxidation and acetone deethanization
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Reaction pathways of Sc~+ (~3D, ~1D) and Fe+ (~6D, ~4F) with acetone in the gas phase: Metal ion oxidation and acetone deethanization

机译：气相中Sc〜+（〜3D，〜1D）和Fe +（〜6D，〜4F）与丙酮的反应途径：金属离子氧化和丙酮脱乙烷

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摘要

The reactions of Sc+ (~3D, ~1D) and Fe + (~6D, ~4 F) with acetone have been investigated in both high- and low-spin states using density functional theory. Our calculations have indicated that oxidation of Sc+ by acetone can take place by (1) metal-mediated H migration, (2) direct methyl-H shift and/or (3) C = O insertion. The most energetically favorable pathway is metal-mediated H migration followed by intramolecular ScO~+ rotation and dissociation. For the deethanization of acetone mediated by Fe~+, the reaction occurs on either the quartet or sextet surfaces through five elementary steps, i.e. encounter complexation, C-C bond activation, methyl migration, C-C coupling and non-reactive dissociation. The rate-determining step along the quartet-state potential-energy surface (PES) is similar to that in the case of Ni~+ (~2 F, 3d~9), namely the methyl-migration step. For the sextet-state PES, however, the energy barrier for methyl migration is lower than that for C-C bond activation, and the rate-determining step is C-C coupling. In general, the low-spin-state pathways are lower in energy than the high-spin-state pathways; therefore, the reaction pathways for the oxidation of Sc~+ and the Fe+-mediated deethanization of acetone mostly involve the low-spin states.
机译：使用密度泛函理论研究了高自旋态和低自旋态下Sc +（〜3D，〜1D）和Fe +（〜6D，〜4 F）与丙酮的反应。我们的计算表明，丙酮可氧化Sc +，可能是由于（1）金属介导的H迁移，（2）直接的甲基H移位和/或（3）C = O插入。在能量上最有利的途径是金属介导的H迁移，随后是分子内ScO〜+旋转和解离。对于Fe〜+介导的丙酮的脱乙烷作用，反应通过五个基本步骤在四重奏或六重奏表面发生，即遇到络合，C-C键活化，甲基迁移，C-C偶联和非反应性离解。沿四重态势能面（PES）的速率确定步骤与Ni〜+（〜2 F，3d〜9）的情况相似，即甲基迁移步骤。然而，对于六重态PES，甲基迁移的能垒比C-C键激活的能垒低，并且速率确定步骤是C-C偶联。通常，低自旋态途径的能量要低于高自旋态途径。因此，Sc〜+的氧化反应和Fe +介导的丙酮脱乙烷反应路径主要涉及低自旋态。

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