The reaction of Os^＋ （^6D, ^4F） with N20 has been investigated at B3LYP/TZVP and CCSD（T）/6-311＋G^＊ levels of theory. The mechanisms corresponding to O-atom and N-atom transfer reactions have been revealed. It w...The reaction of Os^＋ （^6D, ^4F） with N20 has been investigated at B3LYP/TZVP and CCSD（T）/6-311＋G^＊ levels of theory. The mechanisms corresponding to O-atom and N-atom transfer reactions have been revealed. It was found that on the sextet reaction surface both the O-atom and N-atom transfer reactions undergo through direct-abstraction mechanism, leading to the formation of OsO^＋ and OsN^＋, whereas on quartet surface the two reactions undergo through O-N bond or N-N bond insertion mechanism. The calculated energetics shows that the reactions on the sextet surface have notable energy barriers, whereas the reactions on quartet surface are barrierless. ？2009 Xiao Guang Xie. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
基金supported by the Key Laboratory of Forest Resources Conservation and Use in the Southwest Mountains of China(Southwest Forestry University)the National Natural Science Foundation of China(No.20563005)the General Program of the Applied Basic Research of Science and Technology Department of Yunnan Province.
文摘The reaction of Os^＋ （^6D, ^4F） with N20 has been investigated at B3LYP/TZVP and CCSD（T）/6-311＋G^＊ levels of theory. The mechanisms corresponding to O-atom and N-atom transfer reactions have been revealed. It was found that on the sextet reaction surface both the O-atom and N-atom transfer reactions undergo through direct-abstraction mechanism, leading to the formation of OsO^＋ and OsN^＋, whereas on quartet surface the two reactions undergo through O-N bond or N-N bond insertion mechanism. The calculated energetics shows that the reactions on the sextet surface have notable energy barriers, whereas the reactions on quartet surface are barrierless. ？2009 Xiao Guang Xie. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
