Reactivity of Pt- and Pd-bound nitriles towards nitrile oxides and nitrones: substitution vs.cycloaddition

Abstract

Reactions of the nitrone CH₃CHN(CH₃)O and the nitrile oxide CH₃CNO with the nitrile complexes trans-[MCl₂(NCCH₃)₂] (M = Pt, 1; Pd, 2) were investigated by theoretical methods at B3LYP and, for some processes, CCSD(T) levels of theory. The mechanisms of substitutions and cycloadditions were studied in detail. The former occur via a concerted asynchronous mechanism of dissociative type. The calculations of the metal–ligand bond energies in the starting complexes and substitution products and the analysis of structural features of the transition states indicate that the M–N bond dissociation (rather than M–O bond formation) is the step, which controls the reactivity of 1 and 2 in substitutions. The different chemical behaviours of the Pt and Pd complexes towards the 1,3-dipoles were investigated. The exclusive isolation of cycloaddition rather than substitution products in any solvents in the case of 1 is both kinetically and thermodynamically controlled. The switch of the reaction mode from cycloaddition to substitution for 2 in CH₂Cl₂ solution is caused by the significantly lower Pd–N bond energy in comparison with the Pt–N bond energy, consistent with the higher lability of the Pd complexes. The different chemical behaviour of 2 in CH₃CN and CH₂Cl₂solvents is accounted for by the great excess of acetonitrile in the CH₃CN solution rather than a different solvation character. The relative variation of Wiberg bond indices along the reaction path is proposed as a quantitative criterion for the classification of the reaction mechanism.