Ab initio study of bonding between nucleophilic species and the nitroso group

The bonding between anionic nucleophiles and the nitroso group has been studied in the common nitrosating agents nitroso chloride (ONCl), nitroso bromide (ONBr), nitroso thiocyanate (ONSCN), and dinitrogen trioxide (N2O3) in aqueous solution. A variety of theoretical methods were employed, including ab initio, density functional theory (DFT), and composite theoretical techniques, with solvent effects described using the polarizable continuum model (PCM). Experimental nitroso bond heterolytic dissociation free energies were accurately reproduced with a number of composite theoretical methods, the most successful being CBS-Q and G2MP2, with average errors of 3.1 and 3.4 kJ mol(-1), respectively. Using the MP2 and B3LYP methods, calculations were made with correlation consistent basis sets up to quadruple-zeta, extrapolated to the complete basis set (CBS) limit. The MP2/CBS calculations were accurate to around 10 kJ mol(-1), while the B3LYP/CBS calculations routinely overpredicted experimental bond free energies by ca. 40 kJ mol(-1). It is therefore highly recommended that B3LYP energies are not used for nitroso compounds, although other results demonstrate that the B3LYP method provides a good account of nitroso compound geometries, frequencies, and entropies. Single-point CBS energy calculations using MP2/aug-cc-pVQZ geometries and frequencies showed that the MP4(SDTQ) and QCISD(T) methods provide a slight improvement over MP2 at the CBS limit, although the inclusion of triple excitations is necessary to achieve this improvement in accuracy. Enthalpy-entropy compensation was also discovered, with an average isoequilibrium temperature of 825 K. This relatively large isoequilibrium temperature indicates that enthalpic effects dominate over entropic ones.