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

Incorporation of chlorides in coordination complexes, prepared by reactions in CHCl₃, stimulated MP2 and DFT studies of its complete hydrolysis mechanisms. In excellent agreement with previous experimental results, the most important mechanism for CHCl₃ basic hydrolysis at room temperature is the radical one producing :CCl₂. The latter inserts into the H-O bond of H₂O yielding dichloromethanol (<b>1</b>). The hydrolysis mechanism of α-H-lacking PhCCl₃ to the corresponding dichloro(phenyl)methanol (<b>3</b>) was also studied. <b>1</b> decomposes by H₂O to formyl chloride (<b>2</b>) and HCl. <b>2</b>, following a variety of pathways, leads to known CHCl₃ hydrolysis products, such as CO (<b>4</b>) and formic acid (<b>6</b>), via the intermediates chloromethanediol (<b>5</b>), <i>s-cis</i>, <i>s-trans</i>-dihydroxycarbene (<b>ct</b>-<b>7</b>), and <i>s</i>-<i>trans</i>, <i>s</i>-<i>trans</i>-dihydroxycarbene (<b>tt-7</b>). Interestingly, both <b>ct</b>-<b>7</b> and <b>tt-7</b> intermediates have recently been implicated in the reduction of CO₂ with H₂ to <b>6</b>. 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 CHCl₃, 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.