In this chapter, we presented a short review of past and present experimental and theoretical work on the reactions of the transition metal monoxide and dioxide molecules with monochloromethane in excess argon matrices. A series of infrared absorption spectra combining with density functional theoretical (DFT) calculation characterized that the transition metal monoxide molecules produced by laser-ablated higher oxides activated C─H and C─Cl bonds of CH3Cl to first form the weakly bound MO(CH3Cl) (M = Sc, Y, Nb, Ta, Ti, Zr, Mn, Fe) complexes, which further photoisomerized to the more stable chlorine-transfer (Cl-transfer) CH3OMCl (M = Sc, Y), CH3M(O)Cl (M = Ti, Zr), CH3MOCl (M = Mn, Fe), and agostic hydrogen-transfer (H-transfer) CH2ClMOH (M = Sc, Y, Nb, Ta) products upon limited light excitation. Transition metal dioxides reaction with CH3Cl also formed MO2(CH3Cl) (M = Ti, Zr, Nb, Ta) complexes, which were further rearranged to the more stable Cl-transfer CH3OM(O)Cl (M = Ti, Zr) and agostic H-transfer CH2ClM(O)OH (M = Nb, Ta) molecules between the metal center atom and the chlorine atom upon ultraviolet light irradiation. Their different reactivity was interpreted according to the different valence electrons of metal center.
Part of the book: Applications of Molecular Spectroscopy to Current Research in the Chemical and Biological Sciences