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As the overall turnover-limiting step (TOLS) in the homogeneous conversion of N2O, the oxygen-atom transfer (OAT) from an N2O to an Ru-H complex to generate an N2 and Ru-OH complex has been comprehensively investigated by density functional theory (DFT) computations. Theoretical results show that the proton transfer from Ru-H to the terminal N of endo N2O is most favorable pathway, and the generation of N2 via OAT is accomplished by a three-step mechanism [N2O-insertion into the Ru-H bond (TS-1-2, 24.1 kcal mol−1), change of geometry of the formed (Z)-O-bound oxyldiazene intermediate (TS-2-3, 5.5 kcal mol−1), and generation of N2 from the proton transfer (TS-3-4, 26.6 kcal mol−1)]. The Gibbs free energy of activation (ΔG‡) of 29.0 kcal mol−1 for the overall turnover-limiting step (TOLS) is determined. With the participation of potentially existing traces of water in the THF solvent serving as a proton shuttle, the Gibbs free energy of activation in the generation of N2 (TS-3-4-OH2) decreases to 15.1 kcal mol−1 from 26.6 kcal mol−1 (TS-3-4). To explore the structure–activity relationship in the conversion of N2O to N2, the catalytic activities of a series of Ru-H complexes (C1–C10) are investigated. The excellent linear relationships (R2 > 0.91) between the computed hydricities (ΔGH−) and ΔG‡ of TS-3-4, between the computed hydricities (ΔGH−) and the ΔG‡ of TOLS, were obtained. The utilization of hydricity as a potential parameter to predict the activity is consistent with other reports, and the current results suggest a more electron-donating ligand could lead to a more active Ru-H catalyst.

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.