We present here a systematic theoretical study to explore the underlying mechanisms of the H abstraction reaction from methane. Various abstracting agents have been modeled, using oxygen radicals and a set of high val...We present here a systematic theoretical study to explore the underlying mechanisms of the H abstraction reaction from methane. Various abstracting agents have been modeled, using oxygen radicals and a set of high valence metal oxo compounds. Our calculations demonstrate that although H abstraction from CH3-H by metal oxoes can be satisfactorily fitted into the Polanyi correlation on the basis of oxygen radicals, the mechanisms behind are significantly different. The frontier orbital analyses show that there are three electrons and three active orbitals (3e, 3o) involved in H abstraction by oxygen radicals; whereas an additional orbital of pi(M-O)* is involved in H abstraction by M = O, resulting in a (4e, 4o) interaction. In terms of valence bond state correlation diagram, we find that H abstraction by a metal oxo may benefit from the contribution of ionic resonance structures, which could compensate the penalty of opening the M-O pbond. We believe that these findings can help to design more effective catalysts for the activation of light alkanes. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.展开更多
基金financial support from the National Nature Science Foundation of China (21133004,21373167,21573178)the Fundamental Research Funds for the Central Universities (20720160046)the Program for Innovative Research Team in Chinese Universities (IRT_14R31)
文摘We present here a systematic theoretical study to explore the underlying mechanisms of the H abstraction reaction from methane. Various abstracting agents have been modeled, using oxygen radicals and a set of high valence metal oxo compounds. Our calculations demonstrate that although H abstraction from CH3-H by metal oxoes can be satisfactorily fitted into the Polanyi correlation on the basis of oxygen radicals, the mechanisms behind are significantly different. The frontier orbital analyses show that there are three electrons and three active orbitals (3e, 3o) involved in H abstraction by oxygen radicals; whereas an additional orbital of pi(M-O)* is involved in H abstraction by M = O, resulting in a (4e, 4o) interaction. In terms of valence bond state correlation diagram, we find that H abstraction by a metal oxo may benefit from the contribution of ionic resonance structures, which could compensate the penalty of opening the M-O pbond. We believe that these findings can help to design more effective catalysts for the activation of light alkanes. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.
