Theoretical Study on the Reaction of FeS^+(~6Σ^+,~4Ф) with COS in the Gas Phase  

作　　者：张令霞 胡栋宝 杨晓梅 马舒野 李涛洪 谢小光 

机构地区：[1]Department of Chemistry,Yunnan University [2]Yunnan University of Traditional Chinese Medicine [3]Faculty of Chemistry,Southwest Forestry University [4]Key Laboratory of Medicinal Chemistry for Natural Resource(Yunnan University),Ministry of Education 650091,China

出　　处：《Chinese Journal of Structural Chemistry》2010年第12期1848-1856,共9页结构化学（英文）

基　　金：Supported by NNSFC (20563005);the General Program of the Applied Basic Research of Science and Technology Department of Yunnan Province (No. 2008ZC095)

摘　　要：The possible reaction mechanisms of FeS＋（6Σ＋ and 4Ф states） with COS in the gas phase have been studied by using density functional theory at the B3LYP/TZVP and B3LYP/6-311＋G＊ levels：the O/S exchange reaction（FeS＋ ＋ COS=FeO＋ ＋ CS2）,O-transfer reaction（FeS＋ ＋ COS=FeSO＋ ＋ CS） and S-transfer reaction（FeS＋ ＋ COS=FeS2＋ ＋ CO）.The calculation results show that the large barriers（205.7 and 310.1 kJ/mol） and the small probability of forming the preceding intermediate indicate a much lower efficiency of the O/S exchange and the O-transfer reactions and their corresponding products may not be observed experimentally.FeS2＋,the product of S-transfer reaction,is predicted to be the main product.But the reactivity of the 6Σ＋ ground state of FeS＋ toward COS is lower than the earlier transition metal sulfide cations MS＋（M=Sc,Ti and V）,although it has more reaction channels and different mechanisms.The possible reaction mechanisms of FeS＋（6Σ＋ and 4Ф states） with COS in the gas phase have been studied by using density functional theory at the B3LYP/TZVP and B3LYP/6-311＋G＊ levels：the O/S exchange reaction（FeS＋ ＋ COS=FeO＋ ＋ CS2）,O-transfer reaction（FeS＋ ＋ COS=FeSO＋ ＋ CS） and S-transfer reaction（FeS＋ ＋ COS=FeS2＋ ＋ CO）.The calculation results show that the large barriers（205.7 and 310.1 kJ/mol） and the small probability of forming the preceding intermediate indicate a much lower efficiency of the O/S exchange and the O-transfer reactions and their corresponding products may not be observed experimentally.FeS2＋,the product of S-transfer reaction,is predicted to be the main product.But the reactivity of the 6Σ＋ ground state of FeS＋ toward COS is lower than the earlier transition metal sulfide cations MS＋（M=Sc,Ti and V）,although it has more reaction channels and different mechanisms.

关 键 词：iron sulfide cation COS reaction mechanism B3LYP 

分 类 号：O611.3[理学—无机化学]