RESUMO
This work addresses the pathological behavior of the energetics of dimethyl sulfoxide and related sulfur-containing compounds by providing the computational benchmark energetics of R2E2 species, where R = H/CH3 and E = O/S, with bent and pyramidal geometries using state-of-the-art methodologies. These 22 geometries were fully characterized with coupled-cluster with single, double, and perturbative triple excitations [CCSD(T)], second-order Møller-Plesset perturbation theory (MP2), and 22 density functional theory (DFT) methods with 8, 12, and 12, respectively, correlation consistent basis sets of double-, triple-, or quadruple-ζ quality. The relative energetics were determined at the MP2 and CCSD(T) complete basis set (CBS) limits using 17 basis sets up to sextuple-ζ and include augmented, tight-d, and core-valence correlation consistent basis sets. The relative energies of oxygen-/sulfur-containing compounds exhibit exceptionally slow convergence to the CBS limit with canonical methods as well as significant basis set dependence. CCSD(T) with quadruple-ζ basis sets can give qualitatively incorrect relative energies. Explicitly correlated MP2-F12 and CCSD(T)-F12 methods dramatically accelerate the convergence of the relative energies to the CBS limit for these problematic compounds. The F12 methods with a triple-ζ quality basis set give relative energies that deviate no more than 0.41 kcal mol-1 from the benchmark CBS limit. The correlation consistent Composite Approach (ccCA), ccCA-TM (TM for transition metals), and G3B3 deviated by no more than 2 kcal mol-1 from the benchmark CBS limits. Relative energies for oxygen-/sulfur-containing systems fully characterized with DFT are quite unreliable even with triple-ζ quality basis sets, and 13 out of 45 combinations fortuitously give a relative energy that is within 1 kcal mol-1 on average from the benchmark CCSD(T) CBS limit for these systems.
RESUMO
The correlation consistent Composite Approach for transition metals (ccCA-TM) and density functional theory (DFT) computations have been applied to investigate the fluxional mechanisms of cyclooctatetraene tricarbonyl chromium ((COT)Cr(CO)3) and 1,3,5,7-tetramethylcyclooctatetraene tricarbonyl chromium, molybdenum, and tungsten ((TMCOT)M(CO)3 (M = Cr, Mo, and W)) complexes. The geometries of (COT)Cr(CO)3 were fully characterized with the PBEPBE, PBE0, B3LYP, and B97-1 functionals with various basis set/ECP combinations, while all investigated (TMCOT)M(CO)3 complexes were fully characterized with the PBEPBE, PBE0, and B3LYP methods. The energetics of the fluxional dynamics of (COT)Cr(CO)3 were examined using the correlation consistent Composite Approach for transition metals (ccCA-TM) to provide reliable energy benchmarks for corresponding DFT results. The PBE0/BS1 results are in semiquantitative agreement with the ccCA-TM results. Various transition states were identified for the fluxional processes of (COT)Cr(CO)3. The PBEPBE/BS1 energetics indicate that the 1,2-shift is the lowest energy fluxional process, while the B3LYP/BS1 energetics (where BS1 = H, C, O: 6-31G(d'); M: mod-LANL2DZ(f)-ECP) indicate the 1,3-shift having a lower electronic energy of activation than the 1,2-shift by 2.9 kcal mol-1. Notably, PBE0/BS1 describes the (CO)3 rotation to be the lowest energy process, followed by the 1,3-shift. Six transition states have been identified in the fluxional processes of each of the (TMCOT)M(CO)3 complexes (except for (TMCOT)W(CO)3), two of which are 1,2-shift transition states. The lowest-energy fluxional process of each (TMCOT)M(CO)3 complex (computed with the PBE0 functional) has a ΔG of 12.6, 12.8, and 13.2 kcal mol-1 for Cr, Mo, and W complexes, respectively. Good agreement was observed between the experimental and computed 1H-NMR and 13C-NMR chemical shifts for (TMCOT)Cr(CO)3 and (TMCOT)Mo(CO)3 at three different temperature regimes, with coalescence of chemically equivalent groups at higher temperatures.
