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

Incorporation of chlorides in coordination complexes,\nprepared\nby reactions in CHCl<sub>3</sub>, stimulated MP2 and DFT studies of\nits complete hydrolysis mechanisms. In excellent agreement with previous\nexperimental results, the most important mechanism for CHCl<sub>3</sub> basic hydrolysis at room temperature is the radical one producing\n:CCl<sub>2</sub>. The latter inserts into the H–O bond of H<sub>2</sub>O yielding dichloromethanol (<b>1</b>). The hydrolysis\nmechanism of α-H-lacking PhCCl<sub>3</sub> to the corresponding\ndichloro(phenyl)methanol (<b>3</b>) was also studied. <b>1</b> decomposes by H<sub>2</sub>O to formyl chloride (<b>2</b>) and HCl. <b>2</b>, following a variety of pathways, leads\nto known CHCl<sub>3</sub> hydrolysis products, such as CO (<b>4</b>) and formic acid (<b>6</b>), via the intermediates chloromethanediol\n(<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\nrecently been implicated in the reduction of CO<sub>2</sub> with H<sub>2</sub> to <b>6</b>. The conversion of CO to HCOOH was studied.\nMost of the reactions studied are asynchronous concerted processes,\nthe radical mechanism being a multistep one. The synthetic utility\nof this mechanism is briefly mentioned. To avoid chloride ions when\nperforming reactions in CHCl<sub>3</sub>, we should use the solvent\nat room temperature even in the presence of water. This has been verified\nfurther by coordination chemistry reactions in progress.