Abstract
The interaction of CH3Cl/CD3Cl or CH2Cl2/CD2Cl2 with the carborane acid H(CHB11Cl11) (abbreviated as H{Cl11}) generates the salts of CH3-{Cl11} and CH2Cl-{Cl11} and their deuterio analogs, respectively, which are analogs of the salts of asymmetric chloronium cations. Next, salts of chloronium cations CH3-Cl(+)-CH3, ClCH2-Cl(+)-CH2Cl, and ClCH2-Cl(+)-CH3 and their deuterio analogs were obtained from the above compounds. The asymmetric ClCH2-Cl(+)-CH3 cation was found to be unstable, and at ambient temperature, slowly disproportionated into symmetric cations (CH3)2Cl(+) and (CH2Cl)2Cl(+). At a high temperature (150 °C), disproportionation was completed within 5 minutes, and the resulting cations further decomposed into CH3-{Cl11} and CH2Cl-{Cl11}. The molecular fragment ClCH2-(X) of the compounds (X = {Cl11}, -Cl(+)-CH2Cl, or -Cl(+)-CH3) is involved in exchange reactions with CH2Cl2 and CHCl3, converting into CH3-(X) with the formation of chloroform and CCl4, respectively.
Highlights
The interaction of CH3Cl/CD3Cl or CH2Cl2/CD2Cl2 with the carborane acid H(CHB11Cl11) generates the salts of CH3Cl - (CH3)–{Cl11} and CH2Cl–{Cl11} and their deuterio analogs, respectively, which are analogs of the salts of asymmetric chloronium cations
Chloronium salts and IR spectra The CH3–Cl+–CH2Cl cation was obtained by introducing the CH2Cl2 vapors at a partial pressure (PCH2Cl2) of 0.4 atm into an evacuated IR cell containing a film of CH3–{Cl11} sublimed on their Si-windows
After 40 minutes, the spectrum of the cation was isolated by subtracting the original spectrum of CH3–{Cl11} multiplied by the scaling factor f = 0.933 (Fig. 1, red)
Summary
To explore the chemical processes involving chloronium ions by means of IR spectroscopy, their detailed IR spectra must be obtained and interpreted. To continue reactions (4) and (5) at a higher speed, the CH2Cl2 vapors were reintroduced into our IR cell at higher partial pressure (1 atm) The bands indicative of the cation CH3–Cl+– CH2Cl at 1261 and 1248 cmÀ1 made an appearance (Table 2) and increased in intensity We will denote this cation as compound III. The difference in IR spectra before and after the evacuation represented the spectrum of removed molecules It consists of a strong absorption pattern of the original dichloromethane, the characteristic band at 1219 cmÀ1 of chloroform, and a weak band at 790 cmÀ1, which may belong to the C–Cl stretch of CCl4.
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