Bonding in and gas-phase pyrolysis of the arsoranes and stibanes EMe3X2(E = As or Sb, X = F or Cl) and SbMe4F: ultraviolet photoelectron and field-ionization mass spectrometric studies
作者:Susanne Elbel、Helge Egsgaard、Lars Carlsen
DOI:10.1039/dt9870000481
日期:——
The He I (and partially He II) photoelectron spectra of the gaseous Group 5 molecules AsMe3F2, AsMe3Cl2, SbMe3F2, SbMe3Cl2, and SbMe4F are presented and assigned using the known ionization potentials of SbMe5 and EMe3(E = As or Sb) and simple molecular-orbital models. Calculations have been performed for the series AsH3, AsH5, AsH3F2 using the SCC–Xα method. Upon pyrolysis both AsMe3Cl2 and SbMe3Cl2 undergo
使用已知的电离势表示并分配了气态5族分子AsMe 3 F 2,AsMe 3 Cl 2,SbMe 3 F 2,SbMe 3 Cl 2和SbMe 4 F的He I(和部分He II)光电子能谱。SbMe 5和EMe 3(E = As或Sb)和简单的分子轨道模型。已使用SCC-Xα方法对AsH 3,AsH 5,AsH 3 F 2系列进行了计算。热解后,AsMe 3 Cl 2和SbMe3 Cl 2在气相中经历了HCl的单分子消除,表明新的瞬态物质'EMe 3 Cl 2 - n HCl'处于中间状态。然而,气态氟化物有利于MeF的还原消除。这些结果在相似条件下得到了高温场电离质谱的有力支持。在真空中离子PMe 3 Cl 2的固态热解过程中也观察到HCl的损失。