The Generation of Low-Valence Tin Derivatives, RSn(I), in the Gas-Phase by Neutralization—reionization Mass Spectrometry

2002 ◽  
Vol 8 (5) ◽  
pp. 351-357 ◽  
Author(s):  
Dmitri Zagorevskii ◽  
Yang Yuan ◽  
C. Michael Greenlief ◽  
Alexander A. Mommers
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Quantum Chemical Calculations ◽  
Molecular Species ◽  
Quantum Chemical ◽  
Mass Spectra ◽  
Stable Species ◽  
The Stability ◽  
Franck Condon

Neutralization-reionization mass spectrometry (NRMS) was applied to the generation and characterization of low-valence Sn(I) derivatives. The observation of recovery signals in the NR mass spectra of RSn+ ions (R=H, Cl, Br, CH3, C2H, C6H5) demonstrated that their neutral counterparts are stable species in the gas-phase with a lifetime of at least 5 μs. According to quantum chemical calculations, a favorable Franck–Condon factor may contribute to the stability of RSn neutrals generated in the NR event. The experimental results for tin acetylide and phenyltin are the first examples of the generation of these previously unknown molecular species.

Consecutive Methane Activation Mediated by Single Metal Boride Cluster Anions NbB4−

2021 ◽  
Author(s):  
Ying Li ◽  
Ming Wang ◽  
Yongqi Ding ◽  
Chongyang Zhao ◽  
Jia-Bi Ma
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Room Temperature ◽  
Methane Activation ◽  
Cluster Ions ◽  
Metal Boride ◽  
Cluster Anions ◽  
Phase Cluster

Cleavage all C−H bonds in two methane molecules by gas-phase cluster ions at room temperature is a challenging task. Herein, mass spectrometry and quantum chemical calculations have been used to...

scholarly journals Thermodynamics of reactions of ClHg and BrHg radicals with atmospherically abundant free radicals

2012 ◽  
Vol 12 (7) ◽  
pp. 17887-17911
Author(s):  
T. S. Dibble ◽  
M. J. Zelie ◽  
H. Mao
Keyword(s):  
Gas Phase ◽  
Quantum Chemical ◽  
Molecular Level ◽  
Elemental Mercury ◽  
Published Data ◽  
Quantum Calculations ◽  
Laboratory Studies ◽  
Gaseous Elemental Mercury ◽  
The Stability

Abstract. Quantum calculations are used to determine the stability of reactive gaseous mercury (Hg(II)) compounds likely to be formed in the Br-initiated oxidation of gaseous elemental mercury (Hg(0)). Due to the absence of any evidence, current models neglect the possible reaction of BrHg• with abundant radicals such as NO, NO2, HO2, ClO, or BrO. The present work demonstrates that BrHg• forms stable compounds, BrHgY, with all of these radicals except NO. Additional calculations on the analogous ClHgY compounds reveal that the strength of the XHg-Y bond (for X=Cl, Br) varies little with the identity of the halogen. Calculations further suggest that ClO, BrO, and NO3 do not form strong bonds with Hg(0), and cannot initiate Hg(0) oxidation in the gas phase. The theoretical approach is validated by comparison to published data on HgX2 compounds, both from experiments and highly refined quantum chemical calculations. Quantum calculations on the stability of the anions of XHgY are carried out in order to aid future laboratory studies aimed at molecular-level characterization of gaseous Hg(II) compounds. Spectroscopic data on BrHg• are analyzed to determine the equilibrium constant for its formation, and BrHg• is determined to be much less stable than previously estimated. An expression is presented for the rate constant for BrHg• dissociation.

scholarly journals Thermodynamics of reactions of ClHg and BrHg radicals with atmospherically abundant free radicals

2012 ◽  
Vol 12 (21) ◽  
pp. 10271-10279 ◽  
Author(s):  
T. S. Dibble ◽  
M. J. Zelie ◽  
H. Mao
Keyword(s):  
Gas Phase ◽  
Quantum Chemical ◽  
Molecular Level ◽  
Elemental Mercury ◽  
Published Data ◽  
Quantum Calculations ◽  
Laboratory Studies ◽  
Gaseous Elemental Mercury ◽  
The Stability

Abstract. Quantum calculations are used to determine the stability of reactive gaseous mercury (Hg(II)) compounds likely to be formed in the Br-initiated oxidation of gaseous elemental mercury (Hg(0)). Due to the absence of any evidence, current models neglect the possible reaction of BrHg with abundant radicals such as NO, NO2, HO2, ClO, or BrO. The present work demonstrates that BrHg forms stable compounds, BrHgY, with all of these radicals except NO. Additional calculations on the analogous ClHgY compounds reveal that the strength of the XHg-Y bond (for X = Cl, Br) varies little with the identity of the halogen. Calculations further suggest that HO2 and NO3 do not form strong bonds with Hg(0), and cannot initiate Hg(0) oxidation in the gas phase. The theoretical approach is validated by comparison to published data on HgX2 compounds, both from experiment and highly refined quantum chemical calculations. Quantum calculations on the stability of the anions of XHgY are carried out in order to aid future laboratory studies aimed at molecular-level characterization of gaseous Hg(II) compounds. Spectroscopic data on BrHg is analyzed to determine the equilibrium constant for its formation, and BrHg is determined to be much less stable than previously estimated. An expression is presented for the rate constant for BrHg dissociation.

scholarly journals Ion mobility separation of deprotonated oligosaccharide isomers – evidence for gas-phase charge migration

2016 ◽  
Vol 52 (83) ◽  
pp. 12353-12356 ◽  
Author(s):  
W. B. Struwe ◽  
C. Baldauf ◽  
J. Hofmann ◽  
P. M. Rudd ◽  
K. Pagel
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Quantum Chemical Calculations ◽  
Ion Mobility ◽  
Quantum Chemical ◽  
Ion Mobility Mass Spectrometry ◽  
Charge Migration ◽  
Mobility Separation ◽  
Ion Mobility Separation

Ion mobility-mass spectrometry in combination with quantum chemical calculations provides evidence that the charge in deprotonated glycan ions is mobile.

scholarly journals Synthesis of Bis(Carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) and Attempt of Synthesis of Gadolinium Bis(Dicarbollide)

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1321
Author(s):  
Yasunobu Asawa ◽  
Aleksandra V. Arsent’eva ◽  
Sergey A. Anufriev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Single Crystal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
X Ray Diffraction ◽  
Stable Conformation ◽  
Acyl Chlorides ◽  
X Ray ◽  
Cesium Fluoride ◽  
The Stability

Bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) were prepared by the reactions of the corresponding carboranyl acyl chlorides with ethylenediamine. Crystal molecular structure of 1,1′-μ-(CH2NH(O)C-1,2-C2B10H11)2 was determined by single crystal X-ray diffraction. Treatment of bis(carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 with ammonium or cesium fluoride results in partial deboronation of the ortho-carborane cages to the nido-carborane ones with formation of [7,7′(8′)-μ-(CH2NH(O)C(CH2)n-7,8-C2B9H11)2]2−. The attempted reaction of [7,7′(8′)-μ-(CH2NH(O)CCH2-7,8-C2B9H11)2]2− with GdCl3 in 1,2-dimethoxy- ethane did not give the expected metallacarborane. The stability of different conformations of Gd-containing metallacarboranes has been estimated by quantum-chemical calculations using [3,3-μ-DME-3,3′-Gd(1,2-C2B9H11)2]− as a model. It was found that in the most stable conformation the CH groups of the dicarbollide ligands are in anti,anti-orientation with respect to the DME ligand, while any rotation of the dicarbollide ligand reduces the stability of the system. This makes it possible to rationalize the design of carborane ligands for the synthesis of gadolinium metallacarboranes on their base.

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