“Marriage” of Inorganic to Organic Chemistry as Motivation for a Theoretical Study of Chloroform Hydrolysis Mechanisms

Abstract

Incorporation of chlorides in coordination complexes, prepared by reactions in CHCl 3 , stimulated MP2 and DFT studies of its complete hydrolysis mechanisms. In excellent agreement with previous experimental results, the most important mechanism for CHCl 3 basic hydrolysis at room temperature is the radical one producing :CCl 2 . The latter inserts into the H−O bond of H 2 O yielding dichloromethanol (1). The hydrolysis mechanism of α-H-lacking PhCCl 3 to the corresponding dichloro(phenyl)methanol (3) was also studied. 1 decomposes by H 2 O to formyl chloride (2) and HCl. 2, following a variety of pathways, leads to known CHCl 3 hydrolysis products, such as CO (4) and formic acid (6), via the intermediates chloromethanediol (5), s-cis, s-trans-dihydroxycarbene (ct-7), and s-trans, s-trans-dihydroxycarbene (tt-7). Interestingly, both ct-7 and tt-7 intermediates have recently been implicated in the reduction of CO 2 with H 2 to 6. The conversion of CO to HCOOH was studied. Most of the reactions studied are asynchronous concerted processes, the radical mechanism being a multistep one. The synthetic utility of this mechanism is briefly mentioned. To avoid chloride ions when performing reactions in CHCl 3 , we should use the solvent at room temperature even in the presence of water. This has been verified further by coordination chemistry reactions in progress.