Firouzbakht Marjan, Zhou Shaodong, González-Navarrete Patricio, Schlangen Maria, Kaupp Martin, Schwarz Helmut
Institut für Chemie, Technische Universität Berlin, Straβe des 17. Juni 135, 10623, Berlin, Germany.
Chemistry. 2017 Sep 7;23(50):12346-12352. doi: 10.1002/chem.201701615. Epub 2017 Jun 21.
The thermal gas-phase reactions of methane with [OMoH] and [MoH] were investigated by using electrospray-ionization mass spectrometry (ESI-MS) complemented by quantum-chemical calculations. In contrast to the inertness of [MoH] towards methane, [OMoH] activates the C-H bond to form the ionic product [OMo(CH )] concomitantly with the liberation of H . The origin of the varying reactivities is traced back to a different influence of the oxo ligand on the Mo-C and Mo-H bonds. While the presence of this ligand weakens both the Ti-H and the Ti-CH bonds, both the Mo-H and Mo-CH bonds are strengthened. The more pronounced strengthening of the Mo-CH bond compared to the Mo-H bond favors the exothermicity of the reaction of [OMoH] with CH .
采用电喷雾电离质谱法（ESI-MS）并辅以量子化学计算，研究了甲烷与[OMoH]和[MoH]的热气相反应。与[MoH]对甲烷的惰性不同，[OMoH]激活C-H键，形成离子产物[OMo(CH )]，同时释放出H 。反应活性变化的根源可追溯到氧代配体对Mo-C键和Mo-H键的不同影响。虽然该配体的存在会削弱Ti-H键和Ti-CH键，但Mo-H键和Mo-CH键都会得到加强。与Mo-H键相比，Mo-CH键的强化更为显著，这有利于[OMoH]与CH 反应的放热性。
