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.
Spectrochim Acta A Mol Biomol Spectrosc. 2013 Dec;116:96-101. doi: 10.1016/j.saa.2013.07.010. Epub 2013 Jul 10.
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.
采用基质隔离红外光谱法和量子化学计算研究了铁和锰的一氧化物（FeO 和 MnO）分子与一氯甲烷在固体氩气中的反应。在退火过程中，FeO 和 MnO 与 CH3Cl 的反应首先形成 OM-(η(Cl)-CH3Cl)（MMn，Fe）配合物，当 300<λ<580nm 照射时，该配合物可异构化为 CH3MOCl（MMn，Fe）。通过用 CD3Cl 和 (13)CH3Cl 进行同位素 IR 研究和密度泛函计算对产物进行了表征。基于理论计算，OFe-(η(Cl)-CH3Cl) 和 OMn-(η(Cl)-CH3Cl) 配合物分别具有 Cs 对称的 (5)A'和 (6)A'基态。CCSD(T)单点精确计算表明，CH3MOCl 的异构化能比 OM-(η(Cl)-CH3Cl)（MMn，Fe）配合物分别低 13.8 和 3.1 kcal/mol。
