The Thermochemistry of Alkyne Insertion into a Palladacycle outlines the Solvation Conundrum in DFT.

In an effort to determine the thermochemistry of established organometallic transformation, well documented reaction alkynes with a palladacycle was investigated by isothermal titration calorimetry (ITC). Although mechanism insertion unsaturated substrates into Pd−C bond cyclopalladated compounds is known, no information available so far about their thermochemistry. The enthalpies reactions Ph−C≡C−Ph and MeOC(O)−C≡C(O)COMe bisacetonitrilo salt N,N-benzylamine were determined ITC in chlorobenzene after having optimized conditions ensure that only double single occurring respectively. energy profile DFT for process involving confirmed earlier conclusions on rate determining character first insertion. Further computations reveal significant discrepancies between DFT-D/continuum solvation enthalpies, are suspected arise from unexpected explicit noncovalent interaction PhCl components reaction.