Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China.
Rapid Commun Mass Spectrom. 2011 Jan 15;25(1):169-78. doi: 10.1002/rcm.4848.
Electrospray ionization triple quadrupole mass spectrometry (ESI-TSQ-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) were used to investigate the interesting gas-phase reactions of the cationic iron (Fe) complexes of 2-pyrimidinyloxy-N-arylbenzylamines (1-6), which are generated by ESI when mixing their methanolic solutions. Further studies of these Fe complexes by collision-induced dissociation (CID) show that Fe(III) complexes undergo an interesting gas-phase single electron transfer (SET) reaction to give 1(•+) -6(•+) ,with loss of neutral FeCl(2) , whereas Fe(II) can catalyze gas-phase Smiles rearrangement reactions of compounds 1-6. By using different Fe(II)X(2) salts (X = Cl or Br) with a set of reactants, the role of the counterion (X(-) ) and the structure effect of the reactants on Fe(II)-catalyzed gas-phase Smiles rearrangement reactions are studied. Evidence obtained from by TSQ-MS and FTICR-MS experiments, hydrogen/deuterium (H/D) exchange experiments and theoretical computations supported some unique gas-phase chemistries initiated by introduction of Fe(II) into 1. Importantly, by comparing the distinct gas-phase reaction results of the cationic Fe(III) complexes with those of Fe(II) complexes, the charge state effects of iron on the gas-phase chemistries of Fe complexes are revealed.
电喷雾电离三重四极杆质谱 (ESI-TSQ-MS) 和电喷雾电离傅里叶变换离子回旋共振质谱 (ESI-FTICR-MS) 被用于研究有趣的气相反应，即阳离子铁 (Fe) 配合物 2-嘧啶氧基-N-芳基苄基胺 (1-6) 的气相反应，这些配合物是通过混合它们的甲醇溶液时的电喷雾而产生的。通过碰撞诱导解离 (CID) 对这些 Fe 配合物的进一步研究表明，Fe(III) 配合物经历了有趣的气相单电子转移 (SET) 反应，生成 1(•+) -6(•+) ，同时失去中性 FeCl(2) ，而 Fe(II) 可以催化化合物 1-6 的气相 Smiles 重排反应。通过使用不同的 Fe(II)X(2)盐 (X = Cl 或 Br) 与一组反应物，研究了反离子 (X(-) ) 的作用以及反应物的结构效应对 Fe(II)催化的气相 Smiles 重排反应的影响。通过 TSQ-MS 和 FTICR-MS 实验、氢/氘 (H/D) 交换实验和理论计算获得的证据支持了一些独特的气相化学，这些化学是通过向 1 中引入 Fe(II)而引发的。重要的是，通过比较阳离子 Fe(III)配合物与 Fe(II)配合物的明显气相反应结果，揭示了铁的价态对 Fe 配合物气相化学的影响。
