Neutralization—reionization mass spectrometry as a novel probe to structurally characterize organic ligands generated in the Fe(I)-mediated oligomerization of acetylene in the gas phase

Schröder, Detlef; Sülzle, Detlev; Hrušák, Jan; Böhme, Diethard K.; Schwarz, Helmut

doi:10.1016/0168-1176(91)80023-g

Cited by 86 publications

(49 citation statements)

References 46 publications

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“…As shown in Figure 3 + . With regard to the structures of the neutral products, the present data do not permit a more definitive assignment, because more sophisticated mass spectrometric experiments for the characterization of neutral transitionmetal species formed in gas-phase reactions [55,56] cannot be applied in this particular case for instrumental circumstances. On the basis of analogies between the ionic and neutral products and additional thermochemical considerations outlined below, we tentatively propose the occurrence of Reactions (16), (17), and (18).…”

Section: Ion/molecule Reactions With Nomentioning

confidence: 99%

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

2009

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Electrospray ionization (ESI) of aqueous cobalt(II) and nickel-(II) nitrate solutions inter alia affords the solvated, mono-and oligonuclear nitrato complexes [M m + (M = Co, Ni; m = 1-5; n = 1-4). The collision-induced dissociation spectra of the mass-selected ions imply that these ions correspond to genuine hydrated metal(II) nitrato complexes in that either cluster degradation through expulsion of neutral M(NO 3 ) 2 or sequential loss of water ligands take place. In the case of the lowest member of the series (m, n = 1), however, loss of water competes with homolytic cleavage of the N-O bond, which leads to the formation of [M,O 2 ,H 2 ] + cat-

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Section: Ion/molecule Reactions With Nomentioning

confidence: 99%

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

2009

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“…Another interesting question is whether a complex of the form Fe(C2H2)3 + will go towards the formation of benzene in a concerted mechanism or will it prefer to go through a cyclobutadiene or metallacycle complex, Fe(C2H2)(C4H4) + and then form benzene? We also want to understand why, in the experiment (35), no Fe(C4H4) + products are observed whereas the C4H4 unit seems to be an important reaction intermediate in the cyclotrimerization of acetylene on the Pd(lll) surface (4%~45) and on a U + cation (37).…”

Section: Internal Proton Transfer In Malonaldehydementioning

confidence: 98%

“…Acetylene oligomerization with Fe + Cyclotrimerization of acetylene in the gas phase induced by transition metal atoms (35)(36)(37), clusters (38)(39)(40) and surfaces (41~45) is being studied intensively, but the reaction mechanism is still unknown. In particular, Irion et al (38)(39)(40) showed experimental evidence that when ethylene reacts with Fe4 + , a product of stoechiometry Fe^CeHe)" 1 ' is formed through dehydrogenation of ethylene, and benzene is released during the collision-induced dissociation experiment.…”

Section: Internal Proton Transfer In Malonaldehydementioning

confidence: 99%

“…In the proposed mechanism, it is acetylene rather than ethylene that is adsorbed on the Fe4 + cluster. In order to improve our knowledge of this reaction and to characterize some reaction intermediates, we initiated calculations, first, on a smaller system, the Fe + -mediated oligomerization of acetylene in the gas phase (35). The immediate goal is to obtain equilibrium structures for the following complexes; Fe(C2H 2 ) + , Fe(C 2 H 2 ) 2 + , Fe(C 2 H 2 ) 3 + and Fe(C 6 H 6 )+ and the transition states between them.…”

Section: Internal Proton Transfer In Malonaldehydementioning

confidence: 99%

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Performance of Density Functional for Transition States

Salahub

Chrétien

Milet

et al. 1999

ACS Symposium Series

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An overview of the performance of GGA, hybrid and LAP density functionals for transition states in a variety of benchmark systems is given. Examples, such as hydrogen abstraction and intramolecular proton transfer in malonaldehyde, illustrate the difficulties which even the most advanced density functionals meet in describing transition states. Comparisons are also reported for the oligomerization of acetylene Fe(C 2 H 2 ) + 2 --> Fe(C 4 H 4 ) + .Advances in computational techniques and the vast experience of the past decades have allowed an understanding of catalytic reactions at a very detailed level, involving full geometry optimization, characterization of transition states (TS) and reaction intermediates (1-3). The contemporary methods of density functional theory (DFT), especially with the latest progress in the development of efficient exchange-correlation (XC) functionals, appear rather successful in these cases, embodying a large amount of electron correlation at a much lower computational cost (1-3). However, in some cases the reaction path and especially the structure and the energy of the TS may present a stringent test for the existing approximate XC functionals. A typical example is the hydrogen abstraction reaction going through one of the seemingly simplest TS structures, a linear three-atomic complex. The correct reproduction of the energy barrier for this reaction turns out to be a very difficult task not only for approximate DFT methods but also for Hartree-Fock (HF) and most of the post-HF ab initio methods (4,5). In this chapter we shed some light on why this linear three-center TS structure is so difficult to describe.Another big challenge for DFT and post-HF methods is the correct description of inter-molecular and intra-molecular proton transfer (PT) energetics. The energy barrier for the internal proton transfer (IPT) in malonaldehyde is particularly difficult

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“…Subsequently, an 8-keV beam of B(l)E( 1) mass-selected ions of the elemental composition [Fe,C6,H6,0]' was subjected to a neutralization-re-ionization (NR) experiment [ 191 using c-C3H6/0, as collision gases (80% transmission for each collision). Recent studies [20] indicated that NRMS might be valuable in probing the bonding properties of organometallic systems in the gas phase.…”

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confidence: 99%

Benzene Oxidation by ‘Bare’ FeO⁺ in the Gas Phase

Schröder

Schwarz

1992

Helvetica Chimica Acta

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Bare FeO+ reacts in the gas phase with benzene at collision rate (k = 1.3 × 10−9 cm3 molecule−1 s−1), giving rise to the formation of Fe(C6H4)+/H2O(5%), Fe(C5H6)+/CO(37%), Fe(C5H5)+/CO/H. (2%), and Fe+/C6H5OH (56%). Neither the reaction rate nor the product distribution are subject to a significant kinetic isotope effect, thus, ruling out several mechanistic variants described in the literature to the operative for ‘analogous’ arene oxidation processes in solution. A mechanism is suggested which is in keeping with the experimental findings, and which also accounts for some remarkable results obtained, when two [Fe, C6,H6H6O]+ isomers are generated and subjected to a neutralization‐re‐ionization experiment in the gas phase.

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Neutralization—reionization mass spectrometry as a novel probe to structurally characterize organic ligands generated in the Fe(I)-mediated oligomerization of acetylene in the gas phase

Cited by 86 publications

References 46 publications

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

Performance of Density Functional for Transition States

Benzene Oxidation by ‘Bare’ FeO⁺ in the Gas Phase

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Neutralization—reionization mass spectrometry as a novel probe to structurally characterize organic ligands generated in the Fe(I)-mediated oligomerization of acetylene in the gas phase

Cited by 86 publications

References 46 publications

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO3)2 (M = Co, Ni) into Metal–Oxo Species

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO3)2 (M = Co, Ni) into Metal–Oxo Species

Performance of Density Functional for Transition States

Benzene Oxidation by ‘Bare’ FeO+ in the Gas Phase

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Product

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Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

Gas‐Phase Model Studies Relevant to the Decomposition of Transition‐Metal Nitrates M(NO₃)₂ (M = Co, Ni) into Metal–Oxo Species

Benzene Oxidation by ‘Bare’ FeO⁺ in the Gas Phase