"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 (1). The hydrolysis mechanism of α-H-lacking PhCCl3 to the corresponding dichloro(phenyl)methanol (3) was also studied. 1 decomposes by H2O to formyl chloride (2) and HCl. 2, following a variety of pathways, leads to known CHCl3 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 CO2 with H2 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 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.