Reactions of Hf+, Ta+, and W+ with O2 and CO: Metal carbide and metal oxide cation bond energies

Hinton, Christopher; Li, Fengxia; Armentrout, P. B.

doi:10.1016/j.ijms.2008.08.025

Cited by 49 publications

(64 citation statements)

References 72 publications

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“…Exothermic and efficient formation of the tantalum oxide cation occurs readily in the reaction of Ta + ( 5 F) with O2 (efficiency 100 ± 20% or 82 ± 25%) [26,27] and with H2O (efficiency 13 ± 4%) [28], and is essentially impossible to eliminate entirely. and without IR exposure.…”

Section: Resultsmentioning

confidence: 99%

“…The TaO + species has been examined theoretically by Hinton et al and was found to have a 3 Δ ground state with low-lying 1 Δ and 1 Σ + states 0.575 and 0.816 eV higher in energy for B3LYP/HW+/6-311+G(3df) calculations, respectively [29]. Given D0(TaO + ) = 7.10 ± 0.12 eV [26], formation of TaO + ( 3 ∆) from the reactions of Ta + with O2 and H2O are exothermic by 1.98 ± 0.12 and 2.07 ± 0.12 eV, respectively, consistent with the efficiency of these reactions as studied previously [26][27][28][29]. Notably, this exothermicity also means that the singlet excited states are plausibly formed as well.…”

Section: Reaction Coordinate Pathway For Tao + + C2h4mentioning

confidence: 99%

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Metallacyclopropene structures identified by IRMPD spectroscopic investigation of the dehydrogenation reactions of Ta+ and TaO+ with ethene

Wheeler

Coates

Lapoutre

et al. 2019

International Journal of Mass Spectrometry

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Species formed in the reactions of Ta + and TaO + with ethene are examined spectroscopically using infrared multiple photon dissociation (IRMPD) action spectroscopy. Ta + , TaC2H2 + , and TaO + are all observed to dehydrogenate ethene yielding [Ta,2C,2H] + , [Ta,4C,4H] + , and [Ta,O,2C,2H] + , respectively. For these species, IR action spectra are obtained in the 225 -3400 cm -1 range by monitoring fragmentation into the [Ta,2C] + , [Ta,4C,nH] + (n = 2, 3), and [Ta,O] + mass channels, respectively. The spectra are assigned to TaC2H2 + , Ta(C2H2)2 + , and OTaC2H2 + metallacyclopropene species on the basis of comparisons with scaled vibrational spectra from B3LYP/def2-TZVPPD geometry optimized structures. To further elucidate the chemistry observed, complete reaction coordinate pathways having quintet, triplet, and singlet spin for all three dehydrogenation reactions have also been examined.

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Section: Resultsmentioning

confidence: 99%

Section: Reaction Coordinate Pathway For Tao + + C2h4mentioning

confidence: 99%

Metallacyclopropene structures identified by IRMPD spectroscopic investigation of the dehydrogenation reactions of Ta+ and TaO+ with ethene

Wheeler

Coates

Lapoutre

et al. 2019

International Journal of Mass Spectrometry

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“…This work reveals the energetics, kinetics, and dynamics of the interaction of the rhenium metal cation with O 2 . In previous studies in our laboratory, GIBMS has been used to systematically study the kinetic energy dependent reactions of O 2 with atomic cations of the first-row, [13][14][15][16][17][18][19][20][21] second-row, 15,16,[22][23][24][25][26][27] and third-row transition metals 16,[28][29][30][31][32][33] and main group metals. [34][35][36] In many cases, analyses of the cross sections for the analogues of reaction (1) have enabled determination of the BDEs of the metal oxide cation, MO + .…”

Section: Introductionmentioning

confidence: 99%

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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“…For the MH + species, more accurate thermochemistry is obtained from examining the reaction of M + with H 2 (and its deuterated isotopologues), because in the H 2 system there is no competition with another low energy channel, whereas competition with reaction (1) occurs in the methane system. In addition, MC + bond energies have also been obtained from the reaction of M + with CO for M + =Hf + , Ta + , and W + , and from photodissociation of AuCH 2 + . The results of this work are compiled in Table and the periodic trends illustrated in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…In 2013, Lapoutre et al utilized infraredm ultiple photon dissociation (IRMPD) action spectroscopy to experimentally interrogate the structures of MCH 2 + species formed by methane dehydrogenation with M + = Ta + ,W + ,I r + ,a nd Pt + . [19] Notably, because these are four atom systems, the extento fi ntramolecular vibrational redistribution( IVR) is limited,s uch that the free La + [7] 239 (9) [47a] 499 (8) 405 (6) 223 (14) Lu + [7] 200 (15) [47a] 400 (18) > 234 (5) 183 (20) Hf + [11] 204 (8) [47b] 308 (3) [48] 492 (14) 422 (7) 205 (24) Ta + [12] 231 (8) [47c] 366 (4) [48] 562 (15) 464 (3) 260 (14) Ta 2 + [23] 523 (18) > 454 328 (15) W + [13] 219 (5) [47c] 463 (8) [48] 580 (27) 456 (4) 223 (10) Re + [14] 221 (7) (7) 209 (23) [a] Values obtained from the references noted for each metale xcepta sn oted;u ncertaintiesi np arentheses.…”

Section: Structuresmentioning

confidence: 99%

Methane Activation by 5 d Transition Metals: Energetics, Mechanisms, and Periodic Trends

Armentrout

2016

Chemistry A European J

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Although it has been known for almost three decades that several 5d transition-metal cations will activate methane at room temperature, a more detailed examination of these reactions across the periodic table has only recently been completed. In this Minireview, we compare and contrast studies of the kinetic energy dependence of these reactions as studied using guided-ion-beam tandem mass spectrometry. Thermochemistry for the various products observed (MH , MH , MC , MCH , MCH , and MCH ) are collected and periodic trends evaluated and discussed. The mechanisms for the reactions as elucidated by synergistic quantum chemical calculations are also reviewed. Recent spectroscopic evidence for the structures of the MCH dehydrogenation products are discussed as well.

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Reactions of Hf+, Ta+, and W+ with O2 and CO: Metal carbide and metal oxide cation bond energies

Cited by 49 publications

References 72 publications

Metallacyclopropene structures identified by IRMPD spectroscopic investigation of the dehydrogenation reactions of Ta+ and TaO+ with ethene

Metallacyclopropene structures identified by IRMPD spectroscopic investigation of the dehydrogenation reactions of Ta+ and TaO+ with ethene

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

Methane Activation by 5 d Transition Metals: Energetics, Mechanisms, and Periodic Trends

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