Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstrasse 40, 24098 Kiel, Germany.
Chemistry. 2013 Mar 11;19(11):3741-50. doi: 10.1002/chem.201203459. Epub 2013 Jan 25.
Reactions of M(+) (H2 O)n (M=V, Cr, Mn, Fe, Co, Ni, Cu, Zn; n≤40) with NO were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Uptake of NO was observed for M=Cr, Fe, Co, Ni, Zn. The number of NO molecules taken up depends on the metal ion. For iron and zinc, NO uptake is followed by elimination of HNO and formation of the hydrated metal hydroxide, with strong size dependence. For manganese, only small HMnOH(+) (H2 O)n-1 species, which are formed under the influence of room-temperature black-body radiation, react with NO. Here NO uptake competes with HNO formation, both being primary reactions. The results illustrate that, in the presence of water, transition-metal ions are able to undergo quite particular and diverse reactions with NO. HNO is presumably formed through recombination of a proton and (3) NO(-) for M=Fe, Zn, preferentially for n=15-20. For manganese, the hydride in HMnOH(+) (H2 O)n-1 is involved in HNO formation, preferentially for n≤4. The strong size dependence of the HNO formation efficiency illustrates that each molecule counts in the reactions of small ionic water clusters.
采用傅里叶变换离子回旋共振（FT-ICR）质谱法研究了 M(+)（H2 O)n（M=V、Cr、Mn、Fe、Co、Ni、Cu、Zn；n≤40）与 NO 的反应。观察到 Cr、Fe、Co、Ni、Zn 与 NO 的吸收。吸收的 NO 分子数取决于金属离子。对于铁和锌，NO 的吸收伴随着 HNO 的消除和水合金属氢氧化物的形成，具有强烈的尺寸依赖性。对于锰，只有在室温黑体辐射的影响下形成的小的 HMnOH(+)（H2 O)n-1 物种才与 NO 反应。在这里，NO 的吸收与 HNO 的形成竞争，两者都是主要反应。结果表明，在水存在的情况下，过渡金属离子能够与 NO 发生相当特殊和多样的反应。HNO 可能通过质子和（3）NO(-)的重组形成，对于 M=Fe、Zn，优先形成 n=15-20。对于锰，HMnOH(+)（H2 O)n-1 中的氢化物参与 HNO 的形成，优先形成 n≤4。HNO 形成效率的强烈尺寸依赖性表明，每个分子在小离子水簇的反应中都很重要。
