Reactions of transition-metal ions with sulfur hexafluoride in the gas phase

Jiao, C.Q.; Freiser, Ben S.

doi:10.1021/ja00067a047

Cited by 24 publications

(59 citation statements)

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“…Note that the thermochemical values in Table VII imply AE͑SF 5 ϩ /SF 6 ͒ ϭ14.30Ϯ0.16 eV, much lower than the value of 15.1 eV adopted in the JANAF tables but consistent with a recent limit AE͑SF 5 ϩ /SF 6 ͒Ͼ14.1Ϯ0.3 eV. 51 In the ion beam experiment, ⌬ f H 0°͑ SF 5 ϩ ͒ is derived from the sum of the five successive bond strengths. 7 Since each bond energy measurement is subject to uncertainty, the ⌬ f H 0°v alue for SF 5 ϩ is the least reliable in the study.…”

Section: G Bond Energy D(sf 5 -F)supporting

confidence: 80%

Structure and thermochemistry of sulfur fluorides SFn (n=1–5) and their ions SF+n (n=1–5)

Irikura¹

1995

The Journal of Chemical Physics

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Section: G Bond Energy D(sf 5 -F)supporting

confidence: 80%

Structure and thermochemistry of sulfur fluorides SFn (n=1–5) and their ions SF+n (n=1–5)

Irikura¹

1995

The Journal of Chemical Physics

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“…Although its contribution to the overall atmospheric greenhouse gas concentration is less than 1%, global levels continue to increase as a result of its commercial use . Several previous studies have examined the chemistry of SF 6 with a number of neutral and ionic species relevant to atmospheric processes. ,− In addition, previous studies of gas phase transition metal ions with SF 6 have been carried out which show that the early metals participate in a range of exothermic fluorine- and fluoride-transfer processes, while the late metals (including Cu + ( 1 S)) are largely unreactive with this molecule under these energetic conditions. , …”

Section: Introductionmentioning

confidence: 99%

State-Specific Reactions of Cu⁺(¹S,³D) with SF₆ and SF₅Cl

2016

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State-specific reactions of Cu(+)((1)S,(3)D) were carried out in a selected ion drift cell apparatus with SF6 and SF5Cl. Copper ions were prepared in a glow discharge utilizing Ne as the working gas. Analysis of Cu(+) states using ion mobility mass spectrometry (IMS) indicated the presence of both Cu(+)(3d(10)) and Cu(+)(3d(9)4s(1)) configurations attributable to the (1)S ground and (3)D first excited states of this metal ion, respectively. State-specific product formation in reactions of these ions with the two neutral substrates of interest here was determined using IMS along with both known and calculated energetic requirements for product formation. These experiments indicate that Cu(+)((1)S) associates with both SF6 and SF5Cl; however, the process is approximately four times as efficient with the latter neutral under these conditions. Association is also observed as a minor product between Cu(+)((3)D) and both neutral reactants. Inefficient formation of SF3(+) occurs as the sole bimolecular product from SF6 via Cu(+)((3)D). In contrast, Cu(+)((3)D) reacts with SF5Cl in rapid parallel bimolecular processes yielding SF3(+) and CuCl(+). These results also indicate that CuCl(+) initiates additional higher-order processes which result in SF5(+) and SF4Cl(+). The energetics associated with the formation of SF3(+) suggest that a copper halide neutral byproduct must also be formed, requiring a more complex mechanism than simple dissociative charge-transfer.

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“…1,2 Early work by Freiser and co-workers explored the reactions of metal-containing cations with a range of neutral reagents with Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry. [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Armentrout and co-workers extensively probed the reactions of atomic and polyatomic metal cations with substrates such as methane, atmospheric gases, and organic molecules employing guided ion-beam mass spectrometry for the determination of accurate reaction energetics. [20][21][22][23][24][25][26][27][28][29] Schwarz, Schröder, Schlangen, and co-workers have long focused on the role of metal cations in catalytic cycles.…”

Section: Introductionmentioning

confidence: 99%