Use of a two-sequential radical reaction scheme to rationalise the high-oxidation-state carbene species detected under confinement conditions for the interactions Fe(⁵D) + CH_4−n F_n (n = 2−4)

Low‐Energy Pathways Found for the NH3 Activation and H2 Elimination by the Werner‐Type Complexes M(NH3)4+ (M=Fe, Ru and Os).

“…For the same reason, reactions along these channels evolve independently to their corresponding products. A similar two‐step reaction scheme has been used to rationalize the shift in the spin multiplicity between the reactants and the observed products for other interactions [33–38] …”

“…Likewise, it was analyzed the viability of using a two‐step reaction scheme involving the formation and recombination of the radical fragments M(NH 3 ) n (H) + +NH 2 (yielded by abstraction of an hydrogen atom by the metallic moiety) to rationalize the formation of the inserted fragments M(NH 3 ) n (H)NH 2 + . A similar two‐step radical reaction scheme has been used in previous contributions to explain for the observed products in other reactions [33–38] . Although mass‐spectrometry determinations on these reactions have inspired the present study, this investigation is mainly focused on the analysis of the factors that could be relevant in determining the role of the metal‐ligand interactions on the NH 3 activation by the ammine complexes yielded by sequential addition of NH 3 ligands to the metallic center.…”

“…A similar two-step radical reaction scheme has been used in previous contributions to explain for the observed products in other reactions. [33][34][35][36][37][38] Although mass-spectrometry determinations on these reactions have inspired the present study, this investigation is mainly focused on the analysis of the factors that could be relevant in determining the role of the metal-ligand interactions on the NH 3 activation by the ammine complexes yielded by sequential addition of NH 3 ligands to the metallic center. However, even when our reaction models do not consider the experimental conditions of the spectroscopic determinations, there is a good agreement between the results presented herein and those obtained by mass spectrometry for the investigated interactions.…”

“…A similar two-step reaction scheme has been used to rationalize the shift in the spin multiplicity between the reactants and the observed products for other interactions. [33][34][35][36][37][38] In Figure 4 are shown the potential energy plots for these recombination reactions. As it is seen in Figure 5, the product Ru(NH 3 ) 3 (H)NH 2 + evolving from the doublet pathway is more stable than that corresponding to the quadruplet one by 38.7 kcal/mol (for both multiplicity-channels a NH 3 ligand is expelled out when the NH 2 group is been attached to the metallic center).…”

Applying a Nonspin-Flip Reaction Scheme to Explain for the Doublet Sulfide Oxides SMO2 Observed for the Reactions of SO2 with V(4F), Nb(6D), and Ta(4F)

“…e low-spin carbenes and carbynes detected in the IR-matrix spectra for the reactions of zirconium, iron, and ruthenium with fluoromethanes were rationalized by means of two sequential radical reactions [26][27][28]. Likewise, in a recent contribution, we have extended the use of this scheme to the description of interactions involving transition-metal complexes.…”