FT-ICR studies of sputtered metal cluster ions. 5. The chemistry of iron cluster cations with ammonia and hydrazine

Irion, Manfred P.; Schnabel, P.

doi:10.1021/j100179a021

Cited by 32 publications

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“…This agreement indicates that the barrier no longer exceeds the endothermicity for reaction ͑4͒ by a significant amount. This is consistent with the observa- [51][52][53] have demonstrated that the iron tetramer cation is much more reactive than other iron clusters, it seems reasonable that there should not be a barrier in excess of the endothermicity for the dehydrogenation reaction by the tetramer.…”

Section: Fe N ¿ -Cdsupporting

confidence: 90%

Activation of methane by size-selected iron cluster cations, Fen+ (n=2–15): Cluster-CHx (x=0–3) bond energies and reaction mechanisms

Liyanage

Zhang

Armentrout

2001

The Journal of Chemical Physics

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Articles you may be interested inMethane activation by cobalt cluster cations, Co n + ( n = 2 -16 ) : Reaction mechanisms and thermochemistry of cluster-CH x ( x = 0 -3 ) complexes J. Chem. Phys. 130, 054309 (2009); 10.1063/1.3073886 Guided ion beam studies of the reactions of Co n + ( n = 1 -18 ) with N 2 : Cobalt cluster mononitride and dinitride bond energies Guided ion-beam studies of the reactions of Co n + ( n = 2 -20 ) with O 2 : Cobalt cluster-oxide and -dioxide bond energies J. Chem. Phys. 123, 064304 (2005); 10.1063/1.1998836 Methane activation by nickel cluster cations, Ni n + (n=2-16): Reaction mechanisms and thermochemistry of cluster-CH x (x=0-3) complexes Guided ion beam studies of the reaction of Ni n + (n=2-16) with D 2 : Nickel cluster-deuteride bond energiesThe kinetic energy dependences of the reactions of Fe n ϩ (nϭ2 -15) with CD 4 are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-10 eV. All reactions exhibit thresholds and two main products, Fe n D ϩ and Fe n CD 2 ϩ , are formed. These primary products decompose at higher energies to form secondary and higher order products, Fe n CD ϩ , Fe n C ϩ , Fe nϪ1 D ϩ , Fe nϪ1 CD 2 ϩ , Fe nϪ1 CD ϩ , and Fe nϪ1 C ϩ . The cross-section magnitudes for the dehydrogenation products, Fe n CD 2 ϩ , are observed to vary considerably as a function of cluster size; subsequent dehydrogenation to form Fe n C ϩ becomes more facile for larger clusters. Thresholds for the various primary and secondary reactions are analyzed and bond energies for iron cluster cation bonds to C, CD, CD 2 , and CD 3 are determined. As a function of cluster size, these bond energies rapidly reach relatively constant values, which are argued to lie close to bulk phase values. The relative magnitudes in these bond energies are consistent with simple bond order considerations. On the basis of this thermochemistry, we find that there are barriers to the primary dehydrogenation reactions for all the clusters, except nϭ3 and 4. Evidence that this barrier for nу5 corresponds to the chemisorption step is discussed.

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Section: Fe N ¿ -Cdsupporting

confidence: 90%

Activation of methane by size-selected iron cluster cations, Fen+ (n=2–15): Cluster-CHx (x=0–3) bond energies and reaction mechanisms

Liyanage

Zhang

Armentrout

2001

The Journal of Chemical Physics

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“…This may occur with and without accompanying loss of an iron atom, leading to Fe3(NH)z(NH3)+ and Fe4(NH)2(NH3)+ with a probability of 65% and 35% respectively. The end products of this sequence are Fe3(NH)z(NH3): and Fe4(NH),(NH3): [30,31].…”

Section: System Fez /Nh3: Dehydrogenation Of Ammoniamentioning

confidence: 99%

“…This has recently been described in detail [31]. Common to all products is a hydrazine fragment added to the cluster ion.…”

Section: System Fez /N2h4: Reactions With Hydrazinementioning

confidence: 99%

“…That is a preparative method to add an N2 ligand onto naked Fe,' clusters, which is impossible by simply exposing them to N2 gas at the low pressures achievable in an ICR cell. Exemplary CID experiments on Fe6N: ions with Xe as a collision gas at center-of-mass energies up to 70 eV revealed that the bonds of the N atoms to each other and to the metal cluster must be of almost equal strength [31]. Course of the reactivity of Fe,+ (n = 2.…”

Section: System Fez /N2h4: Reactions With Hydrazinementioning

confidence: 99%

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Chemical Reactivity. Chemical Reactions of Metal Cluster Cations in a Fourier‐Transform ion Cyclotron Resonance Mass Spectrometer

Irion

Schnabel

1992

Ber Bunsenges Phys Chem

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Adsorption 1 Chemical Kinetics 1 FT-ICR Mass Spectrometry / Ion-Molecule Reactions / Metal ClustersMetal cluster cations are generated in an external ion source by sputtering the respective metal foil with 20 keV Xe+ primary ions and are then injected by a series of electric lenses into the analyzer cell of a home-built Fourier-Transform Ion Cyclotron Resonance Mass Spectrometer (FT-ICR MS). There, they are trapped in a magnetic field of 7 T for several tens of seconds through electrostatic deceleration and pulsed addition of a bath gas. Collisions serve to remove excess kinetic as well as inner energy and cool them to nearly room temperature. By the application of a radio frequency (RF) ejection pulse, one specific ion mass may be isolated. -Chemical reactions of the stored metal cluster ions may be studied by admitting a reactive gas with a continuous leak valve. We have investigated a variety of combinations metal/gas and found often surprising size-specific effects. For some systems, the reactivity as a function of cluster size changes in an abrupt way whereas for others it varies smoothly. Transition metal clusters predominantly show dehydrogenation reactions, the degree of which depends on the nature of the metal as well as on cluster size. In addition, it is demonstrated that naked gas phase metal cluster ions may possess catalytic activity: Fez ions bind up to four molecules of ethene under hydrogen elimination and liberate benzene through collision-induced dissociation at low energy. The assertion of catalysis is proven by a complex sequence of five consecutive mass spectrometry steps (an (MS)' experiment), in which the originally trapped Fez clusters actually do initiate the synthesis of benzene twice.

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“…These studies have been reviewed by Knickelbein. 1) For example, Irion and Schnabel 2) have reported that Fe 4 þ shows high reactivity with ammonia in contrast to their neighboring clusters. The ion/ molecule reactions of metal cluster cations are interesting topics of physical chemistry.…”

Section: Introductionmentioning

confidence: 99%

Ion/Molecule Reactions of Silver Cluster Cations with Crown Ethers in a Cylindrical Ion Trap

Kumondai

Toyoda

Iwamoto

et al. 2004

Jpn. J. Appl. Phys.

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For observing gas-phase ion/molecule reactions of metal cluster cations, a cylindrical ion trap time-of-flight mass spectrometer was newly constructed. This apparatus consists of an external sputtering ion source, ion deceleration lens system, cylindrical ion trap and time-of-flight mass analyzer with four toroidal electric sectors. Using this apparatus, ion/molecule reactions of silver cluster cation, Ag 5 þ , with crown ether, 12-crown-4 (12C4), were observed. The cluster-ligand complexes, [Ag 5 (12C4) n ] þ (n ¼ 1{3) and fragmentations of the cluster induced by adducts of crown ether molecules were also observed.

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FT-ICR studies of sputtered metal cluster ions. 5. The chemistry of iron cluster cations with ammonia and hydrazine

Cited by 32 publications

References 0 publications

Activation of methane by size-selected iron cluster cations, Fen+ (n=2–15): Cluster-CHx (x=0–3) bond energies and reaction mechanisms

Activation of methane by size-selected iron cluster cations, Fen+ (n=2–15): Cluster-CHx (x=0–3) bond energies and reaction mechanisms

Chemical Reactivity. Chemical Reactions of Metal Cluster Cations in a Fourier‐Transform ion Cyclotron Resonance Mass Spectrometer

Ion/Molecule Reactions of Silver Cluster Cations with Crown Ethers in a Cylindrical Ion Trap

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