Mechanistic Aspects and Elementary Steps of NH Bond Activation of Ammonia and CN Coupling Induced by Gas‐Phase Ions: A Combined Experimental/Computational Exercise

Abstract

In the last decades, N-H bond activation of ammonia and C-N coupling processes have formed the focus of broad research activities. More recently, gas-phase experiments combined with computational studies have provided rather detailed insights into the mechanisms and the elementary steps of these two reaction types. Some of the multifarious observations made and results obtained for these two processes mediated by gaseous "bare" or ligated ions are outlined in this review article.

Reactivity of lanthanoid mono-cations with ammonia: A combined inductively coupled plasma mass spectrometry and computational investigation

“…This type of reactions is often called in the literature activation of ammonia N-H bonds by a metallic cation, as well as insertion of metallic cation into a covalent bond. 23,24,28 Up to 5 NH 3 additions were further observed on LnNH + giving LnNH(NH 3 ) n + (n=1-5). In contrast, Eu + and Sm + did not form LnNH + in our experimental conditions (about 10 -5 atm of ammonia).…”

“…Furthermore, chemical reactivity of metal ions is of fundamental interest for the activation of covalent bonds (typically C-H, C-C, C-O, C-F, N-H, N-O), 5,[23][24][25][26][27][28] and for the potential elimination of H 2 associated with some of these activations, which could be used to produce gas phase H 2 .…”

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

“…Reactive intermediates that are often present at very low concentrations can be detected, isolated in the gas phase and can have their reactivity probed. [8][9][10] The structure of the intermediates can be interrogated in collisional experiments or with ion spectroscopy approaches. 11,12 The limitations of ESI-MS always have to be considered.…”

Quantum Chemical Study of the Reactions between Pd+/Pt+ and H2O/H2S

“…The study of the reactivity of bare transition-metal cations in the gas phase is of utmost importance given the role they play in a variety of chemical processes, including the crucial and challenging s-activation process. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Among these studies, the reactions between transitionmetal cations and water have been extensively studied from the pioneering state-specific studies of Armentrout et al, who laid out most of the main issues, [17][18][19] to the recent measurements by Bohme et al, who have compiled their results in a recent report. [20] Additionally, quantum chemistry mechanistic studies performed for the early, [21][22][23] middle, [24,25] and late [26] first-row transition metals agreed with the experimental evidence, [20] which showed that whereas for early first-row transition metals their bare cations are more reactive than their oxides, the opposite is the case for the late transition-metal cations.…”