甲基镧系化合物对水的活化：氢与甲烷的演化

IF 1.8 3区化学 Q4 BIOCHEMICAL RESEARCH METHODS

Rapid Communications in Mass Spectrometry Pub Date : 2025-05-01 DOI:10.1002/rcm.10054

Songpeng Wan, Yu Gong, Xiuting Chen

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引用次数: 0

摘要

镧系烃基配合物在有机合成、催化过程和小分子活化中表现出优异的性能，它们通常在反应性上表现出一些有价值的差异，这些差异可能受到金属中心及其氧化态的影响。金属羧酸盐前驱体的脱羧是获得大量有机金属配合物的有力手段，适合于气相研究，采用电喷雾电离质谱（ESI-MS）实验结合密度泛函理论（DFT）计算。方法采用ESI法在甲醇中制备（CH3CO2）LnCl3−和（CH3CO2）2LnCl2−(Ln = Sm, Eu, Yb)前驱阴离子。采用碰撞诱导解离（CID）技术，通过醋酸镧系氯离子的断裂反应得到（CH3）LnIIICl3−和（CH3）LnIICl2−。通过离子-分子反应（IMR）实验研究了（CH3）LnIIICl3−或（CH3）LnIICl2−通过CH4或H2释放对水分子的活化作用。在DFT计算的支持下，探讨了镧系元素中心及其氧化态的影响。结果（CH3CO2）LnCl3−(Ln = Sm, Eu, Yb)在CID作用下脱羧生成（CH3）LnIIICl3−，而（CH3CO2）2LnCl2−经过连续两步CO2/CH3或一步CH3CO2·和CO2损失生成（CH3）LnIICl2−。三种（CH3）LnIIICl3−阴离子均与H2O自发反应生成Ln (OH)Cl3−并伴有甲烷释放，反应程度一般为（CH3）SmIIICl3−> (CH3)EuIIICl3−> (CH3)YbIIICl3−。对于（CH3）EuIIICl3−与H2O反应，也有少量的（ch30）EuIIICl3−通过氢损失反应生成。三个（CH3）LnIICl2−阴离子通过CH4损失与H2O的反应速度明显快于（CH3）LnIIICl3−，反应活性增强程度为Yb >； Eu > Sm，这与（CH3）LnIICl2−到（CH3）LnIICl2−的Ln-C键延伸趋势一致。此外，（CH3）SmIICl2−和（CH3）YbIICl2−与H2O发生H2损失反应，而（CH3）EuIICl2−则与（CH3）LnIIICl3−相反。结论甲基镧系氯配合物对水的反应活性受镧系中心及其氧化态的显著影响。一般来说，甲基镧系（II）氯配合物（CH3）LnIICl2−比甲基镧系（III）氯配合物（CH3）LnIIICl3−反应性强得多。此外，（CH3）LnIIICl3−的反应活性为Sm >； Eu > Yb, (CH3)LnIICl2−的反应活性为Eu >； Sm≈Yb。

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Water Activation by Methyllanthanides: Hydrogen Versus Methane Evolution

Rationale

The lanthanide hydrocarbyl complexes often exhibit exceptional performance in organic synthesis, catalytic process, and small molecule activation, and they generally exhibit several valuable differences in reactivity which can be influenced by the metal center and its oxidation state. Decarboxylation of metal carboxylate precursor is a powerful means to obtain multitudinous organometallic complexes which are well suited for gas-phase investigation by employing electrospray ionization mass spectrometry (ESI-MS) experiments in combination with density functional theory (DFT) calculations.

Methods

The (CH₃CO₂)LnCl₃⁻ and (CH₃CO₂)₂LnCl₂⁻ (Ln = Sm, Eu, and Yb) precursor anions were produced in the gas phase via ESI of LnCl₃ and CH₃CO₂Na mixtures in methanol. Collision-induced dissociation (CID) technique was employed to obtain (CH₃)Ln^IIICl₃⁻ and (CH₃)Ln^IICl₂⁻ via fragmentation reactions of lanthanide acetate chloride anions. Activation of water molecule by (CH₃)Ln^IIICl₃⁻ or (CH₃)Ln^IICl₂⁻ via CH₄ or H₂ release was investigated by ion-molecule reaction (IMR) experiments. With the support of DFT calculations, the influences of lanthanide center and its oxidation state were also explored.

Results

(CH₃)Ln^IIICl₃⁻ was generated via decarboxylation of (CH₃CO₂)LnCl₃⁻ (Ln = Sm, Eu, and Yb) upon CID, while (CH₃CO₂)₂LnCl₂⁻ underwent consecutive two-step CO₂/CH₃ or one-step CH₃CO₂·and CO₂ losses to give (CH₃)Ln^IICl₂⁻. All three (CH₃)Ln^IIICl₃⁻ anions spontaneously reacted with H₂O to form Ln (OH)Cl₃⁻ accompanied by methane release, and the reaction extent is generally following as (CH₃)Sm^IIICl₃⁻ > (CH₃)Eu^IIICl₃⁻ > (CH₃)Yb^IIICl₃⁻. For (CH₃)Eu^IIICl₃⁻ with H₂O, there was minor (CH₃O)EuCl₃⁻ produced through hydrogen loss reaction as well. Three (CH₃)Ln^IICl₂⁻ anions reacted much more quickly than (CH₃)Ln^IIICl₃⁻ with H₂O via CH₄ loss, and the reactivity enhancement extent is following as Yb > Eu > Sm, which agrees well with Ln-C bond elongation trend from (CH₃)Ln^IIICl₃⁻ to (CH₃)Ln^IICl₂⁻. Moreover, (CH₃)Sm^IICl₂⁻ and (CH₃)Yb^IICl₂⁻ rather than (CH₃)Eu^IICl₂⁻ underwent H₂ loss reaction with H₂O, which is on the contrary with the cases of (CH₃)Ln^IIICl₃⁻.

Conclusion

The reactivity of the methyllanthanide chloride complexes towards water is significantly influenced by the lanthanide center and its oxidation state. In general, the methyllanthanide (II) chloride complexes (CH₃)Ln^IICl₂⁻ is much more reactive than the methyllanthanide (III) chloride complexes (CH₃)Ln^IIICl₃⁻. Besides, the reactivity of (CH₃)Ln^IIICl₃⁻ is following as Sm > Eu > Yb, while that of (CH₃)Ln^IICl₂⁻ is Eu > Sm ≈ Yb.

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来源期刊

Rapid Communications in Mass Spectrometry 化学-分析化学

CiteScore

4.10

自引率

5.00%

发文量

219

审稿时长

2.6 months

期刊介绍： Rapid Communications in Mass Spectrometry is a journal whose aim is the rapid publication of original research results and ideas on all aspects of the science of gas-phase ions; it covers all the associated scientific disciplines. There is no formal limit on paper length ("rapid" is not synonymous with "brief"), but papers should be of a length that is commensurate with the importance and complexity of the results being reported. Contributions may be theoretical or practical in nature; they may deal with methods, techniques and applications, or with the interpretation of results; they may cover any area in science that depends directly on measurements made upon gaseous ions or that is associated with such measurements.