The [Re, O8]+ potential energy surface: fourier transform ion cyclotron resonance collision induced dissociation studies and density functional calculations

Beyer, Martin K.; Berg, Christian; Joos, Stefan; Achatz, Uwe; Hieringer, Wolfgang; Niedner‐Schatteburg, Gereon; Bondybey, V. E.

doi:10.1016/s1387-3806(98)14136-2

Cited by 12 publications

(16 citation statements)

References 45 publications

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“…They suggested that the scheme is initiated by the direct oxidation of Re + with O 2 forming the Re(O 2 ) + isomer. 32 The reaction of the Re(O 2 ) + ion to form ReO 3 + was computed by these authors to be exothermic by 79.8 kcal mol -1 and was shown to proceed in the FT-ICR experiments with 9% efficiency, in remarkable agreement with the value of 9.4% obtained with our experiments. No further kinetic information was obtained in the FT-ICR experiments, but it was proposed that Re(O 2 ) + also reacts with O 2 to initiate an O 2 addition sequence that ultimately forms Re(O 2 ) 4 + and that ReO 3 + forms ReO 3 (O 2 ) + .…”

Section: Resultssupporting

confidence: 84%

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Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity

et al. 2002

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An Inductively-Coupled Plasma/Selected-Ion Flow Tube (ICP/SIFT) tandem mass spectrometer has been employed in a systematic survey of room-temperature reactions of O 2 with 29 transition-metal ions. The atomic ions are produced at ca. 5500 K in an ICP source and are allowed to decay radiatively and to thermalize by collisions with Ar and He atoms prior to reaction. Rate coefficients were measured for the reactions of first-row atomic ions from Sc + to Zn + , of second-row atomic ions from Y + to Cd + (excluding Tc + ) and of third-row atomic ions from La + to Hg + . Both O-atom abstraction and O 2 addition were observed as primary reaction channels. Periodicities in reactivity are identified and are compared with periodicities in the O-atom affinity of the atomic ion. O-atom abstraction was observed to be efficient when exothermic and inefficient when endothermic. NbO + , MoO + , TaO + , and WO + reacted further in a second O-atom transfer reaction with O 2 . ReO 2 + produced by direct addition of O 2 to Re + reacted further by both O-atom abstraction and O 2 addition. Sequential O 2 addition was observed to produce the higher oxides: MO 3 + (M ) Ti, V, Y, Zr, Hf, Os), MO 4 + (M ) Cr, Fe, Co, Ni, Cu, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, Pt, Au), MO 5 + (M ) V, Re, Os), MO 6 + (M ) Nb, W, Re) and MO 7 + (M ) V). Novel termolecular reactions second-order in oxygen were identified for Os + and ZrO + at high oxygen concentrations to produce O 2 + and OsO + from Os + and a neutral metal oxide from Zr + .

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Section: Resultssupporting

confidence: 84%

“…Beyer et al also have provided theoretical insight into the structures and energies for all of these oxide ions. 32 Figure 8 presents our ICP/SIFT observations made with Os + as the reacting ion that show the formation of the oxide ions OsO x + (x ) 2-5). Ground-state Os + appears to react slowly Table 1).…”

Section: Resultsmentioning

confidence: 99%

Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity

et al. 2002

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“…Notably the endothermicity of reaction (1) observed here agrees with the conclusions of Beyer et al 9 and the failure to observe reaction (1) at room temperature by Bohme and co-workers. 10 Our cross sections for reaction (1) at near thermal energy (0.05 eV) can be converted to a rate coefficient at 300 K of (5 ± 2) × 10 −13 cm 3 molecule −1 s −1 , three orders of magnitude smaller than the collision limit and small enough to agree with the failure to observe this process in the previous study.…”

Section: A Reaction Of Re + With Osupporting

confidence: 92%

“…as also concluded by Beyer et al 9 Bohme and co-workers also found that Re + reacts with NO to form ReO n + where n = 1 -4, which they attributed to sequential termolecular reactions forming N 2 O as the neutral product, 11 although this interpretation has been questioned for other metals. 12 Clearly, the thermochemistry of the rhenium oxide cations is not known very well.…”

Section: Introductionmentioning

confidence: 72%

“…8 In a subsequent study by this group, they performed collision-induced dissociation (CID) studies on all these species, reporting bond energies in most cases, along with density functional calculations of these species in their ground electronic states. 9 At present, this study provides the most accurate thermochemistry for ReO 2 + and ReO + , with bond energies for O atom loss of 7.4 ± 2.2 5 and 5.0 ± 1.3 5 eV, respectively. Finally, in inductively coupled plasma/selected ion flow tube (ICP/SIFT) experiments by Bohme and co-workers, Re + was found to react slowly with O 2 to form ReO 2 + by three-body association, with subsequent additions of oxygen yielding ReO n + where n = 3-6.…”

Section: Introductionmentioning

confidence: 74%

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The bond energy of ReO+: Guided ion-beam and theoretical studies of the reaction of Re+ (7S) with O2

Armentrout¹

2013

The Journal of Chemical Physics

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The kinetic-energy dependence of the Re(+) + O2 reaction is examined using guided ion-beam mass spectrometry. The cross section for ReO(+) formation from ground state Re(+) ((7)S) is unusual, exhibiting two endothermic features. The kinetic energy dependence for ReO(+) formation is analyzed to determine D0(Re(+)-O) = 4.82 ± 0.05 eV, with the higher energy feature having a threshold 1.35 ± 0.28 eV higher in energy. This bond energy is consistent with much less precise values determined in the literature. Formation of ReO2(+) is also observed with a pressure dependent cross section, establishing that it is formed in an exothermic reaction of ReO(+) with O2. The nature of the bonding for ReO(+) and ReO2(+) is discussed and analyzed primarily using theoretical calculations at the B3LYP/def2-TZVPPD level of theory. The ground state of ReO(+) is identified as either (5)Π or (3)Δ, with the latter favored once estimates of spin-orbit splitting are included. Bond energies for ground state ReO(+) are calculated at this level as well as BP86 and CCSD(T,full) levels using several different basis sets. BP86 theoretical bond energies are higher than the experimental value, whereas B3LYP and CCSD(T,full) values are lower, although estimated spin-orbit corrections increase the latter close to experiment. Potential energy surfaces for the reaction of Re(+) with O2 are also calculated at the B3LYP/def2-TZVPPD level of theory and reveal that ground state Re(+) ((7)S) inserts into O2 by forming a Re(+)(O2) ((5)A") complex which can then couple with additional surfaces to form ground state ReO2(+) ((3)B1). Several explanations for the unusual dual endothermic features are explored, with no unambiguous explanation being evident. As such, this heavy metal system provides a very interesting experimental phenomenon of both adiabatic and nonadiabatic behavior.

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Direct Spectroscopic Confirmation of the Oxygen‐Centered Diradical Character of the Tetraoxidorhenium(VII) Cation [Re(O)₄]⁺

da Silva Santos,

Medel,

Kruse

et al. 2024

Chemistry Methods

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Mononuclear inorganic diradical species are scarce. Here, we confirm, via X‐ray absorption spectroscopy in the gas phase combined with computational studies, the oxygen‐centered diradical character of the tetraoxidorhenium(VII) cation. A dioxido‐superoxido isomer, close in energy to the diradical, is also found, where rhenium appears in its rare oxidation state of +6. Addition of one or two hydrogen atoms to [Re,O4]+ forms hydroxido ligands, and strongly disfavors isomers with any oxygen‐oxygen bond. This adds spectroscopic characterization of the rhenium oxidation state and the nature of ligands to the known ability of [Re,O4]+ to perform two consecutive hydrogen‐atom abstraction reactions from methane, and demonstrates that pentaatomic [Re,O4]+ combines a metal center in its highest oxidation state with two oxygen‐centered radical ligands in a highly reactive species.

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The [Re, O8]+ potential energy surface: fourier transform ion cyclotron resonance collision induced dissociation studies and density functional calculations

Cited by 12 publications

References 45 publications

Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity

Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity

The bond energy of ReO+: Guided ion-beam and theoretical studies of the reaction of Re+ (7S) with O2

Direct Spectroscopic Confirmation of the Oxygen‐Centered Diradical Character of the Tetraoxidorhenium(VII) Cation [Re(O)₄]⁺

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The [Re, O8]+ potential energy surface: fourier transform ion cyclotron resonance collision induced dissociation studies and density functional calculations

Cited by 12 publications

References 45 publications

Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity

Gas-Phase Reactions of Transition-Metal Ions with Molecular Oxygen: Room-Temperature Kinetics and Periodicities in Reactivity

The bond energy of ReO+: Guided ion-beam and theoretical studies of the reaction of Re+ (7S) with O2

Direct Spectroscopic Confirmation of the Oxygen‐Centered Diradical Character of the Tetraoxidorhenium(VII) Cation [Re(O)4]+

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Direct Spectroscopic Confirmation of the Oxygen‐Centered Diradical Character of the Tetraoxidorhenium(VII) Cation [Re(O)₄]⁺