Gas-Phase Reactions of Atomic Gold Cations with Linear Alkanes (C2-C9)
Gas-Phase Reactions of Atomic Gold Cations with Linear Alkanes (C2-C9)
复制标题
原子金阳离子与直链烷烃 (C2-C9) 的气相反应
DOI：
10.1021/acs.jpca.6b03836
复制
发表时间：
2016
影响因子：
2.9
通讯作者：
He Sheng-Gui
中科院分区：
文献类型：
--
作者：
Zhang Ting;Li Zi-Yu;Zhang Mei-Qi;He Sheng-Gui
为了开发合适的烷烃离子化方法，过渡金属离子与烷烃的反应性越来越受到人们的关注。在这项研究中，金阳离子与线性烷烃从乙烷到壬烷（CnH 2n +2，n= 2-9）在温和的条件下的反应已被表征的质谱和密度泛函理论计算。小分子烷烃（n= 2-6）与Au+反应时，乙烷遵循脱氢反应通道，其它烷烃遵循氢化物转移反应通道，生成具有烷烃特征的产物离子，表明Au+可以作为试剂离子从乙烷到己烷中还原烷烃。烷烃链长的强烈依赖性观察的速率常数和反应效率。较大的烷烃（n> 6）发生了广泛的裂解。理论计算结果表明，氢化物转移引起的碎裂发生在AuH释放之后。此外，当反应在高压反应器中进行时，成功地避免了正庚烷的碎裂。这意味着Au+是一个潜在的试剂离子，以消除线性，甚至支链烷烃。
To develop proper ionization methods for alkanes, the reactivity of bare or ligated transition metal ions toward alkanes has attracted increasing interests. In this study, the reactions of the gold cations with linear alkanes from ethane up to nonane (CnH2n+2,n= 2–9) under mild conditions have been characterized by mass spectrometry and density functional theory calculations. When reacting with Au+, small alkanes (n= 2–6) were confirmed to follow specific reaction channels of dehydrogenation for ethane and hydride transfer for others to generate product ions characteristic of the original alkanes, which indicates that Au+can act as a reagent ion to ionize alkanes from ethane ton-hexane. Strong dependence of the chain length of alkanes was observed for the rate constants and reaction efficiencies. Extensive fragmentation took place for larger alkanes (n> 6). Theoretical results show that the fragmentation induced by the hydride transfer occurs after the release of AuH. Moreover, the fragmentation ofn-heptane was successfully avoided when the reaction took place in a high-pressure reactor. This implies that Au+is a potential reagent ion to ionize linear and even the branched alkanes.