OSMIUM-TETROXIDE AND ITS FRAGMENT IONS IN THE GAS-PHASE - REACTIVITY WITH HYDROCARBONS AND SMALL MOLECULES
OSMIUM-TETROXIDE AND ITS FRAGMENT IONS IN THE GAS-PHASE - REACTIVITY WITH HYDROCARBONS AND SMALL MOLECULES
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DOI：
10.1021/ja00183a014
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发表时间：
1989-01-04
影响因子：
15
通讯作者：
BEAUCHAMP, JL
中科院分区：
文献类型：
--
作者：
IRIKURA, KK;BEAUCHAMP, JL
本文用傅里叶变换离子回旋共振光谱法研究了OsO_n ~+（= 0-4）与多种烃类和小分子（包括CH_4、C_2 H_4、C_2 H_6、C_3 H_8、C_4 H_10、H_2、CO、NH_3和SiH_4）的气相离子-分子反应。阴离子化学进行了简要的研究。导出的热化学量包括Z）（0 s +-0）= 100±12，D（0 s 0 +-0）= 105±12，E>（0 s 0 2 +-0）= 105±12，D（0 s 0 3 +-0）= 71±12，E>（0 s 0 3 -0）= 78±14，E>（0 s 0 4 +-H）= 132±3 kcal/mol，D（0 s 0 3 +-0）= 132±3 kcal/mol，（OsO3 +-OH）= 101±16 kcal/mol，PA（OsO4）= 161±2 kcal/mol。观察到许多不同的和新颖的反应。其中包括[2S+ 2S]与H2的环加成、键复分解、氧代转移和氢原子夺取。这些离子也是非常活跃的脱氢试剂;最引人注目的例子是SiH 4连续、完全脱氢为单硅化物、二硅化物和三硅化物。另一个有趣的过程是与NH3的双键复分解，其中一个或两个氧代配体被交换为亚氨基。氧代配体的数量被发现有一个显着的化学效果，机制进行了讨论所观察到的反应。例如，OsO 3+的相对惰性归因于Os（+7）中心不能进行氧化加成。OsO 2+是甲烷和分子氧转化为醛的潜在模型催化剂。
Gas-phase ion-molecule reactions of OsO „+(= 0-4) with a number of hydrocarbons and small molecules, includingCH4, C2H4, C2H6, C3H8, C4Hio, H2, CO, NH3, and SiH4, havebeen investigated by Fourier transform ion cyclotron resonance spectrometry. Anion chemistry was briefly investigated. Thermochemical quantities derived include Z)(0s+-0)= 100±12, D (0s0+-0)= 105±12,£>(0s02+-0)= 105±12, D (0s03+-0)= 71±12,£>(0s03-0)= 78±14,£>(Os04+-H)= 132±3 kcal/mol, D (Os03+-OH)= 101±16 kcal/mol, and PA (Os04)= 161±2 kcal/mol. Many diverse and novel reactions are observed. Among them are [2S+ 2S] cycloaddition with H2, bond metathesis, oxo transfer, and hydrogen atom abstraction. These ions are also extraordinarily active dehydrogenationreagents; the most dramatic example is the sequential, complete dehydrogenation of SiH4 to mono-, di-, and trisilicides. Anotherintriguing process is the double bond metathesis with NH3, in which one or two oxo ligands are exchanged for imido groups. The number of oxo ligands is found to have a striking effect on the chemistry; mechanisms are discussed for the reactions observed. For example, the relative inertness of 0s03+ is attributed to a failure of the Os (+ 7) center to undergo oxidative addition. Os02+ emerges as a potential model catalyst for the conversion of methane and dioxygen to aldehydes.