Ammonia activation by iron: state-specific reactions of Fe+(6D, 4F) with ND3 and the reaction of FeNH+ with D2

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

“…The study of the simple reactions M(NH 3 ) n + +NH 3 , can allow to gain some insight into the role played by the ligands on the reactivity exhibited by these systems (interestingly, these ammine‐complexes resemble the charge and the nitrogen environment surrounding the molybdenum compound reported in reference 4). These interactions have been investigated experimentally and theoretically by several authors [12–32] . Recently, Blagojevic et al.…”

Reaction of M(II) Diaryls (M = Mn or Fe) with Ammonia to Afford Parent Amido Complexes

“…Cooperative action of the multiple metal centers in metal clusters such as {Os 3 (CO) 11 (L)} (L = cyclo-C 6 H 8 , CH 3 CN, or NH 3 ) ,− effectively activates NH 3 to form bridging amido species. Milstein and Hartwig reported the oxidative addition of NH 3 to iridium complexes to afford μ 2 -NH 2 species or terminal amido/hydride complexes. ,, Furthermore, oxidative addition reactions of NH 3 with low-valent main group metal species have been reported. ,, The mechanisms and thermodynamics of NH 3 reactions with transition metal complexes have been investigated by spectroscopy ,− and computational studies. − Nonetheless, little attention has been given to the reactions of first-row mid to late metal complexes, e.g., manganese, iron, cobalt, or nickel complexes with NH 3 , and only limited spectroscopic studies, e.g., guided ion beam tandem mass spectrometry of iron species, have been reported. , We now show that the reactions of two-coordinate M(II) diaryls MAr′ 2 (M = Mn or Fe; Ar′ = C 6 H 3 -2,6-(C 6 H 3 -2,6- i Pr 2 ) 2 ) with NH 3 readily afford rare examples of parent amido derivatives of manganese and iron as the complexes {Ar′Mn(μ-NH 2 )(NH 3 )} 2 ( 1 ) and {Ar′Fe(μ-NH 2 )} 2 ( 2 ) with arene (Ar′H) elimination.…”

“…8,12,14 Furthermore, oxidative addition reactions of NH 3 with low-valent main group metal species have been reported. 16,18,20 The mechanisms and thermodynamics of NH 3 reactions with transition metal complexes have been investigated by spectroscopy 13,[25][26][27][28][29][30] and computational studies. [30][31][32][33][34][35][36][37][38][39][40][41] the reactions of first-row mid to late metal complexes, e.g., manganese, iron, cobalt, or nickel complexes with NH 3 , and only limited spectroscopic studies, e.g., guided ion beam tandem mass spectrometry of iron species, have been reported.…”

Iron cation catalyzed reduction of N2O by CO: gas-phase temperature dependent kinetics

“…Since electronic state specific reactivity has been observed in a large number of reactions, including a variety of reactions involving Fe + , [21][22][23][24][25][26][27] we comment on the likelihood of excited state Fe + in our system. In a separate study, we have indeed observed that some electronically excited Fe + enters the flow tube, 28 which could affect our rate constant measurements for reaction (2) in the current study.…”