Argon matrix isolation study of the thermal and photochemical reaction of with

Abstract

Abstract The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to identify and characterize the initial and secondary products in the thermal and photochemical reactions of OVCl 3 with ( CH 3 ) 2 CO . Initial deposition into argon matrices at 14 K led to the formation, in high yield, of the 1:1 molecular complex. This species appears to be strongly bound, leading to large shifts to certain vibrational modes of both the acid and base subunits. Bands due to the complex were destroyed by near-UV irradiation ( λ>300 nm), and led to the formation of intense product bands. In contrast to previous studies, HCl elimination from an initial complex was not observed. Many possible products were considered, including isomerization, decomposition, addition, and addition followed by fragmentation pathways. The products were identified by the use of isotopic labeling and comparison to theoretical calculations. The primary product was determined to be Cl 3 V ( CH 3 ) OC ( O ) CH 3 , formed through rupture of a C–C bond in ( CH 3 ) 2 CO and addition of the two fragments to OVCl 3 . Possible evidence for a second isomer, slightly higher in energy ( Cl 3 V ( OCH 3 )( C ( O ) CH 3 )) was also found.