Carbonyl chloride fluoride determination

Carbonyl chloride fluoride does not associate in the gas phase [1885], and possesses the expected planar Cj structure. The results of the published structural studies are summarized in Table 16.8 the most reliable determination is the result of the combined electron diffraction and microwave spectroscopic study [1531]. Remarkably, prior to these data being published, the fully optimized geometry calculated by ab initio molecular orbital methods [1532] was demonstrated (correctly) to be far superior to the best experimental results available (see Table 16.8). Rather unfortunately, a more recent ab initio study [2176a] performed rather... 

Ab initio molecular orbital calculations are being used to study the reactions of anionic nucleophiles with carbonyl compounds in the gas phase. A rich variety of energy surfaces is found as shown here for reactions of hydroxide ion with methyl formate and formaldehyde, chloride ion with formyl and acetyl chloride, and fluoride ion with formyl fluoride. Extension of these investigations to determine the influence of solvation on the energy profiles is also underway the statistical mechanics approach is outlined and illustrated by results from Monte Carlo simulations for the addition of hydroxide ion to formaldehyde in water. 

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