Ion-molecule reaction chemistry of Fe+ with NO: excited-versus ground-state reactions

Oriedo, J. V. B.; Russell, David H.

doi:10.1021/ja00071a053

Cited by 18 publications

(26 citation statements)

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“…Interestingly, these monitor reactions revealed that even with our precautions we do have a minor N 2 O impurity, on the order of 1%, a finding that other groups also observed. 36,44 The N 2 O impurity does not affect any of our Fe + or FeO + results appreciably because N 2 O reacts inefficiently with those ions (i.e., ∼3 × 10 −11 and ∼1 × 10 −11 cm 3 s −1 , respectively). 33,35,53 The alternative explanation to impurity is the termolecular mechanism of reaction 3 proposed by the York group.…”

Section: ■ Results and Discussionmentioning

confidence: 79%

“…This is in contrast to the recent results for Fe + by Bohme et al, 27 although it agrees with earlier results in the literature. 27,35,36 Without catalytic reduction of NO, the middle cycle shown in Figure 1 does not proceed, and thus, the overall stepwise reduction of NO 2 to N 2 shown cannot occur. On the basis of our experimental observations and theoretical limits on the termolecular process being at odds with reported rates, we conclude that the previously reported positive results for Fe + + NO are due to a minor NO 2 impurity.…”

Section: + ⎯→ ⎯ + δ °= − ±mentioning

confidence: 99%

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Exploring the Reactions of Fe⁺ and FeO⁺ with NO and NO₂

et al. 2012

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We report for the first time temperature dependences (from 300 to 600 K) of the reactions of Fe(+) and FeO(+) with NO and NO(2). Both ions react quickly with NO(2), and their rate constants have weak negative temperature dependences. The former is consistent with the calculated energy profile along the Fe(+) + NO(2) reaction coordinate. Ground state Fe(+) reacts with NO(2) to produce only FeO(+), while FeO(+) reacts with NO(2) to produce NO(+) exclusively. Certain source conditions produce excited Fe(+), as evidenced by production of primary NO(+), which is endothermic with the ground state by 0.35 eV. The room temperature rate constants are in agreement with previous values. For the reactions of Fe(+) and FeO(+) with NO, we find an upper limit of <1.0 × 10(-12) cm(3) s(-1) for both rate constants, in contrast to a previous report of a rate constant of ∼1.7 × 10(-11) cm(3) s(-1) for Fe(+) + NO. Because this is an endothermic process, the prior report interpreted the reaction as a termolecular process involving two NO molecules; instead, we show that the previous results were likely due to an NO(2) impurity. Implications for other metal cation reactions which have been speculated to occur by the termolecular mechanism are discussed.

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Section: ■ Results and Discussionmentioning

confidence: 79%

Section: + ⎯→ ⎯ + δ °= − ±mentioning

confidence: 99%

Exploring the Reactions of Fe⁺ and FeO⁺ with NO and NO₂

et al. 2012

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“…Concern has been expressed in the literature that ions generated by electron impact might contain a significant population of excited states …”

Section: Methodsmentioning

confidence: 99%

Activation of Silane by W⁺ in the Gas Phase: Fourier-Transform Ion Cyclotron Resonance and ab Initio Theoretical Studies

1996

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The gas-phase reactions of the bare tungsten cation W+ with silane have been investigated using Fourier-Transform Ion Cyclotron Resonance mass spectrometry. Dehydrogenation of a first molecule leads to the formation of WSiH2 +. This ion is itself reactive with a second silane molecule, this time through elimination of 2H2, to form WSi2H2 +. A similar reaction follows, yielding WSi3H2 + as the next product ion, which itself leads to both WSi4H4 + and WSi4H2 +. This seems to initiate two parallel reaction sequences, yielding WSi10H6 + as the major final product, together with a minor amount of WSi10H4 +. CID experiments on the products of the first three reactions were carried out to aid in their structural elucidation. Ab initio calculations at the CASSCF level have been performed in order to derive optimum structures for the first two product ions WSiH2 + and WSi2H2 +, and for the non-observed intermediate WSi2H4 +. The results show that structural isomerism exists for these three ions, due to the versatile bonding capabilities of W+ and Si. The ground state of WSiH2 + is a high-spin (sextet) silylene complex in which there is a dative bond between SiH2 and the metal. For WSi2H4 + there are two low-energy isomers, a covalently bonded metal disilene three-membered ring with a quartet spin state, and a datively bonded metal silylsilylene in a high-spin sextet. It is proposed that the successive ions formed have compact structures, and that the reaction sequence ends when the metal gets trapped into a silicon cage, or alternatively when it no longer has enough nonbonding electrons to insert exothermically into a Si−H bond of a further silane molecule.

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“…The reactivity of NO with Fe + was examined by mass spectrometry, which shows that only excited Fe + reacts with NO. 16 The rate coefficients of the reactions were determined, and the reaction mechanisms were also discussed. 17−21 The kinetics of the association reaction of atomic iron with NO was also studied using laser induced fluorescence in the gas phase.…”

Section: ■ Introductionmentioning

confidence: 99%

Infrared Photodissociation Spectroscopy of Iron Nitrosyl Cation Complexes: Fe(NO)_n⁺ (n = 1–5)

Wang

et al. 2014

J. Phys. Chem. A

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Infrared spectra of mass-selected mononuclear iron nitrosyl cations Fe(NO)n(+) with n = 1-5 and their argon tagged complexes are measured via infrared photodissociation spectroscopy in the nitrosyl stretching frequency region in the gas phase. The structures are established by comparison of the experimental spectra with the simulated spectra derived from density functional calculations. Two IR active bands were observed for the argon-tagged Fe(NO)2(+) and Fe(NO)3(+) complexes, consistent with theoretical predictions that these complexes have bent C(2v) and nonplanar C(3v) symmetry, respectively. The Fe(NO)4(+) complex was characterized to have a completed coordination sphere with 17 electrons containing a bent one-electron NO ligand and three three-electron NO ligands. The Fe(NO)5(+) complex was determined to involve a Fe(NO)4(+) core ion that is solvated by an external NO molecule.

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Ion-molecule reaction chemistry of Fe+ with NO: excited-versus ground-state reactions

Cited by 18 publications

References 1 publication

Exploring the Reactions of Fe⁺ and FeO⁺ with NO and NO₂

Exploring the Reactions of Fe⁺ and FeO⁺ with NO and NO₂

Activation of Silane by W⁺ in the Gas Phase: Fourier-Transform Ion Cyclotron Resonance and ab Initio Theoretical Studies

Infrared Photodissociation Spectroscopy of Iron Nitrosyl Cation Complexes: Fe(NO)_n⁺ (n = 1–5)

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Ion-molecule reaction chemistry of Fe+ with NO: excited-versus ground-state reactions

Cited by 18 publications

References 1 publication

Exploring the Reactions of Fe+ and FeO+ with NO and NO2

Exploring the Reactions of Fe+ and FeO+ with NO and NO2

Activation of Silane by W+ in the Gas Phase: Fourier-Transform Ion Cyclotron Resonance and ab Initio Theoretical Studies

Infrared Photodissociation Spectroscopy of Iron Nitrosyl Cation Complexes: Fe(NO)n+ (n = 1–5)

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Product

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Exploring the Reactions of Fe⁺ and FeO⁺ with NO and NO₂

Exploring the Reactions of Fe⁺ and FeO⁺ with NO and NO₂

Activation of Silane by W⁺ in the Gas Phase: Fourier-Transform Ion Cyclotron Resonance and ab Initio Theoretical Studies

Infrared Photodissociation Spectroscopy of Iron Nitrosyl Cation Complexes: Fe(NO)_n⁺ (n = 1–5)