Ultraviolet photolysis of CH2I2 in methanol: O-H insertion and HI elimination reactions to form a dimethoxymethane product.
Ultraviolet photolysis of low concentrations of CH2I2 in methanol solution found that CH2I2 is converted into dimethoxymethane and some H+ and I- products. Picosecond time-resolved resonance Raman (ps-TR3) experiments observed that the isodiiodomethane (CH2I-I) photoproduct decayed faster as the concentration of methanol increases, suggesting that isodiiodomethane is reacting with methanol. Ab initio calculations indicate isodiiodomethane is able to react with methanol via an O-H insertion/HI elimination to form an iodoether (ICH2-O-CH3) and HI products. The iodoether can then further react via another O-H insertion/HI elimination reaction to form the dimethoxymethane (CH3-O-CH2-O-CH3) observed in the photochemistry experiments. A reaction mechanism consistent with these experimental and theoretical observations is proposed.
Guan
Xiangguo
X
Department of Chemistry, University of Hong Kong, Pokfulam Road, Hong Kong, PRC.
Lin
Xufeng
X
Kwok
Wai Ming
WM
Du
Yong
Y
Li
Yun-Liang
YL
Zhao
Cunyuan
C
Wang
Dongqi
D
Phillips
David Lee
DL