...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C+
【24h】

Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C+

机译：离子自由基化学反应的速度图成像研究：烯丙基自由基与C +反应的电荷转移和碳-碳键形成

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5+, is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5+ -> C3H4+ + H. Approximately 80% of the reaction products are ascribed to charge transfer, with similar to 40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5+ complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5+ complex. More than 75% of the nascent C4H3+ products decay by C-H bond cleavage to yield a C4H2+ species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5+ adduct that is produced when the p-orbital containing the unpaired electron on C+ overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3+ product. The large rearrangement in geometry as the C4H3+ products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2+ species.
机译：我们提出了在2.2 eV的碰撞能量下基态碳阳离子与烯丙基自由基C3H5碰撞的动力学的实验和计算研究。产生烯丙基阳离子C3H5 +的电荷转移在3.08 eV时是放热的，并通过能量共振进行，从而电子转移发生而核速度没有显着变化。产物具有足够的能量以经历C 3 H 5 +-> C 3 H 4 + + H的解离过程。约80％的反应产物归因于电荷转移，其中约40％的产物由于氢原子的损失而衰减。我们还观察到由于新的碳-碳键形成而产生的产物。四碳产物的实验速度空间通量分布关于反应物的质心是对称的，提供了直接证据，表明这些产物是由至少存在几个旋转周期的C4H5 +络合物的形成介导的。初级四碳反应产物是通过从C4H5 +络合物中消除分子氢而形成的。超过75％的新生C4H3 +产物会通过C-H键裂解而降解，从而产生C4H2 +物质。在MP2 / 6-311 + g（d，p）的理论水平上进行的量子化学计算支持形成非平面环状C4H5 +加合物，当C +上包含未配对电子的p轨道与上未配对自旋密度重叠时产生烯丙基的末端碳原子。然后通过从环状中间体中1,2-消除氢分子形成平面环状C4H3 +产物，从而形成产物。形成C4H3 +产物时，几何结构发生了较大的重排，与该产物中的高振动激发相一致，并支持以下观察结果：这些产物中的大多数会衰减形成C4H2 +物质。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号