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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reactions within p-Difluorobenzene/Methanol Heterocluster Ions: A Detailed Experimental and Theoretical Investigation
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Reactions within p-Difluorobenzene/Methanol Heterocluster Ions: A Detailed Experimental and Theoretical Investigation

机译：对二氟苯/甲醇杂原子离子内的反应：详细的实验和理论研究

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摘要

The reactivity of p-difluorobenzene/methanol cluster ions has been investigated by using triple quadrupole mass spectrometry and DFT calculations. The present study was performed in light of a recent investigation of p-difluorobenzene/methanol (P ) F-C6H4-F and M ) CH3OH) heterocluster ions where the solvent-catalyzed formation of p-fluoroanisole (A ) CH3O-C6H4-F) was observed in P(M)2+ clusters and not in PM+ clusters.The results of our mass selected cluster ion study and theoretical calculations confirm that a single extra molecule of methanol can lower the reaction activation energy barrier in agreement with previous work forsmaller clusters (PM+ and P(M)2+). However, we also observe that P(M)3+ and P(M)4+ clusters undergo evaporative loss of neutral methanol to establish the P(M)2+ cluster before reacting. P(M)n>4+ clusters arecapable of reacting through multiple pathways, in some cases generating a 1,4-dimethoxybenzene (B ) CH3OC6H4-OCH3) product via two separate substitution reactions within the same cluster ion. DFT calculations were employed to model the structures of the parent cluster ions, and transition state calculations were used to evaluate the activation energy for the p-fluoroanisole-forming substitution reaction. The calculations suggest that the reaction proceeds through a transition state containing a six-member hydrogen-bonded ring involving a reacting methanol and a second methanol that significantly lowers the activation energy.
机译：通过使用三重四极杆质谱和DFT计算研究了对二氟苯/甲醇簇离子的反应性。本研究是根据对对二氟苯/甲醇（P）F-C6H4-F和M）CH3OH）杂簇离子的最新研究进行的，其中溶剂催化形成对氟苯甲醚（A）CH3O-C6H4-F ）在P（M）2+团簇中观察到，而不是在PM +团簇中。集群（PM +和P（M）2+）。但是，我们还观察到，P（M）3+和P（M）4+团簇在发生反应之前会经历中性甲醇的蒸发损失，从而建立P（M）2+团簇。 P（M）n> 4+簇能够通过多种途径反应，在某些情况下会通过同一簇离子内的两个单独的取代反应生成1,4-二甲氧基苯（B）CH3OC6H4-OCH3）产物。使用DFT计算来建模母簇离子的结构，并使用过渡态计算来评估形成对氟苯甲醚的取代反应的活化能。该计算表明该反应通过包含六元氢键合环的过渡态进行，该六元氢键合环涉及反应的甲醇和显着降低活化能的第二种甲醇。

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