Gas-phase reactions of nitric oxide with atomic lanthanide cations: Room-temperature kinetics and periodicity in reactivity

Blagojevic, Voislav; Flaim, Eric; Jarvis, Michael J. Y.; Koyanagi, Gregory K.; Böhme, Diethard K.

doi:10.1016/j.ijms.2005.11.025

Cited by 23 publications

(30 citation statements)

References 12 publications

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“…The bond energies and ionization energies of the oxidants are given in Table 3. The reactivity of Gd + and Lu + (and other lanthanide cations) with several oxidants-N2O [30], O2 [30], NO [31], D2O [32], and CO2 [33]-have been previously studied by Bohme and co-workers using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer, with concurrent results.…”

Section: Reactions Of M + and Mo + With Oxidants: An Evaluation Of D[mentioning

confidence: 99%

Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO

et al. 2008

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Section: Reactions Of M + and Mo + With Oxidants: An Evaluation Of D[mentioning

confidence: 99%

Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO

et al. 2008

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“…Work by the Bohme group investigated a variety of gasphase reactions involving lanthanide cations, by using an ICP-MS. The reactions of the Lanthanides with a range of gases were studied, including nitric oxide, 31 sulfur hexafluoride 32 and ammonia. 33 In all cases, the periodic trends in reaction efficiency were similar and rationalised in terms of the electron promotion energies of Ln + .…”

Section: Discussionmentioning

confidence: 99%

A study of the application of graphite MALDI to the analysis of lanthanides and deconvolution of the isobaric species observed

Conway

Warren

Gates

2021

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“…29 Schwarz et al refined this model, explaining the trend in lanthanide ion reactivity in terms of a qualitative curve crossing, in which bond activation involves an electronically excited asymptote. 24 Our research group [41][42][43][44] and others 32,35 have shown that the rate of formation of LnO + by exothermic O-atom transfer to Ln + from an O-donor molecule often also correlates strongly with the energy required to promote an electron to achieve a 4f nÀ1 5d 1 6s 1 (or 4f nÀ1 5d 2 ) excited Ln + electronic configuration. The requirement of availability of two non-f electrons in reactions of Ln + cations has been cited as evidence of a bond 63 insertion mechanism.…”

Section: Primary Chemistry: Ln + + Nomentioning

confidence: 99%

“…Of particular interest to our research group is the mechanism of formation of LnO + in gas-phase reactions of bare Ln + cations with oxygen-atom donor molecules. We have previously measured the room-temperature kinetics for reactions of Ln + with potential O-atom donors including nitric oxide, 41 oxygen, 42 nitrous oxide, 42 carbon dioxide, 43 and water. 44 Other groups have measured the kinetics for reactions of Ln + with various alcohols.…”

Section: Introductionmentioning

confidence: 99%

Nitrogen dioxide reactions with atomic lanthanide cations and their monoxides: gas-phase kinetics at room temperature

Jarvis

Blagojevic

Koyanagi

et al. 2010

Phys. Chem. Chem. Phys.

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Results of experimental investigations are reported for the gas-phase kinetics of chemical reactions between nitrogen dioxide (NO(2)) and 14 different atomic cations of the lanthanide series, Ln(+) (Ln = La-Lu, excluding Pm), and their monoxides, LnO(+). Measurements were taken with an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer in helium buffer-gas at a pressure of 0.35 +/- 0.01 Torr and at 295 +/- 2 K. The atomic lanthanide cations were produced at ca. 5500 K in an ICP source and allowed to decay radiatively and to thermalize by collisions with Ar and He atoms prior to reaction with NO(2). The atomic ions were observed to react rapidly with NO(2) with large rate coefficients, k > 2 x 10(-10) cm(3) molecule(-1) s(-1), and almost exclusively by oxygen-atom abstraction to produce lanthanide-oxide LnO(+) cations. In contrast to results of previous studies with many other molecules, the reaction efficiency exhibits essentially no dependence upon the energy required to promote an electron to achieve a d(1)s(1) excited electronic configuration, in which two non-f electrons are available to Ln(+) for chemical bonding. Apparently the radical character of NO(2) (X (2)A(1)) leads to the efficient formation of LnO(+) by the end-on abstraction of an oxygen atom by Ln(+). In the reactions with La(+), Ce(+), Pr(+) and Gd(+) an additional minor channel (less than 2%) leads to the formation of NO(+). The LnO(+) product ions participate in various secondary and higher order reactions with NO(2) resulting in the formation of ions of the type LnO(x)(NO)(y)(NO(2))(z)(+) with x = 1-2, y = 0-2, and z = 0-2, as well as the ions NO(+) and NO(2)(+).

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Gas-phase reactions of nitric oxide with atomic lanthanide cations: Room-temperature kinetics and periodicity in reactivity

Cited by 23 publications

References 12 publications

Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO

Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO

A study of the application of graphite MALDI to the analysis of lanthanides and deconvolution of the isobaric species observed

Nitrogen dioxide reactions with atomic lanthanide cations and their monoxides: gas-phase kinetics at room temperature

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Gas-phase reactions of nitric oxide with atomic lanthanide cations: Room-temperature kinetics and periodicity in reactivity

Cited by 23 publications

References 12 publications

Gas-Phase Oxidation of Cm+ and Cm2+ − Thermodynamics of Neutral and Ionized CmO

Gas-Phase Oxidation of Cm+ and Cm2+ − Thermodynamics of Neutral and Ionized CmO

A study of the application of graphite MALDI to the analysis of lanthanides and deconvolution of the isobaric species observed

Nitrogen dioxide reactions with atomic lanthanide cations and their monoxides: gas-phase kinetics at room temperature

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Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO

Gas-Phase Oxidation of Cm⁺ and Cm²⁺ − Thermodynamics of Neutral and Ionized CmO