title: Matrix isolation infrared spectra, assignment and DFT investigation on reactions of iron and manganese monoxides with CH3Cl.
abstract: The reactions of iron and manganese monoxide molecules (FeO, and MnO) with monochloromethane in solid argon have been studied by matrix isolation infrared spectroscopy and quantum chemistry calculations. When annealing, the reactions of FeO and MnO with CH3Cl first form the OM-(η(Cl)-CH3Cl) (MMn, Fe) complexes, which can isomerize to CH3MOCl (MMn, Fe) upon 300<λ<580 nm irradiation. The products were characterized by isotopic IR studies with CD3Cl and (13)CH3Cl and density functional calculations. Based on theoretical calculations, the OFe-(η(Cl)-CH3Cl) and OMn-(η(Cl)-CH3Cl) complexes have (5)A' and (6)A' ground state with Cs symmetry, respectively. The accurate CCSD(T) single point calculations illustrate the CH3MOCl isomerism are 13.8 and 3.1 kcal/mol lower in energy than the OM-(η(Cl)-CH3Cl) (MMn, Fe) complexes.
authors.affiliation: Department of Chemistry, Engineering Research Center for Eco-dyeing and Finishing of Textiles, Key Laboratory of Advanced Textiles Materials and Manufacture Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018, China. Electronic address: yyzhao@zstu.edu.cn.
authors.forename: Yanying
authors.initials: Y
authors.lastname: Zhao
authors.forename: Kexue
authors.initials: K
authors.lastname: Fan
authors.forename: Yongfei
authors.initials: Y
authors.lastname: Huang
authors.forename: Xuming
authors.initials: X
authors.lastname: Zheng
mesh_terms: D005290:Ferric Compounds / Q000737:chemistry*; D017895:Manganese Compounds / Q000737:chemistry*; D008737:Methyl Chloride / Q000737:chemistry*; D008958:Models, Molecular; D010087:Oxides / Q000737:chemistry*; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared
chemical_list: D005290:Ferric Compounds; D017895:Manganese Compounds; D010087:Oxides; C000499:ferric oxide; C027424:manganese oxide; D008737:Methyl Chloride
keywords: Chemical reaction mechanism; Infrared spectroscopy; Matrix isolation; OM-(η(Cl)-CH(3)Cl) complex; Theoretical calculations