Metal Ion Solvation in the Gas Phase:  The Quest for Higher Oxidation States

2002 ◽  
Vol 106 (35) ◽  
pp. 7993-8005 ◽  
Author(s):  
A. J. Stace
Keyword(s):  
Gas Phase ◽  
Metal Ion ◽  
Oxidation States ◽  
Ion Solvation

Synthesis and hydrolysis of gas-phase lanthanide and actinide oxide nitrate complexes: a correspondence to trivalent metal ion redox potentials and ionization energies

2015 ◽  
Vol 17 (15) ◽  
pp. 9942-9950 ◽  
Author(s):  
Ana F. Lucena ◽  
Célia Lourenço ◽  
Maria C. Michelini ◽  
Philip X. Rutkowski ◽  
José M. Carretas ◽  
...  
Keyword(s):  
Gas Phase ◽  
Metal Ion ◽  
Oxidation States ◽  
Redox Potentials ◽  
Trivalent Metal ◽  
Ionization Energies ◽  
Reduction Potentials ◽  
Hydrolysis Of ◽  
Nitrate Complexes

Gas-phase hydrolysis of lanthanide/actinide MO3(NO3)3−ions relates to the stabilities of the MIVoxidation states, which correlate with IV/III solution reduction potentials and 4th ionization energies.

A molecular picture of metal ion solvation: Infrared spectroscopy of Cu+(NH3)n and Ag+(NH3)n in the gas phase

2009 ◽  
Vol 147 (1-2) ◽  
pp. 71-76 ◽  
Author(s):  
Kazuhiko Ohashi ◽  
Kazuya Inoue ◽  
Takuro Iino ◽  
Jun Sasaki ◽  
Ken Judai ◽  
...  
Keyword(s):  
Infrared Spectroscopy ◽  
Gas Phase ◽  
Metal Ion ◽  
Ion Solvation ◽  
Molecular Picture

Ion chemistry of second-row transition metals in hydrocarbon flames: cations and anions of Y, Zr, Nb, and Mo

1995 ◽  
Vol 73 (12) ◽  
pp. 2263-2271 ◽  
Author(s):  
Christine C.Y. Chow ◽  
John M. Goodings
Keyword(s):  
Transition Metals ◽  
Gas Phase ◽  
Atmospheric Pressure ◽  
Chemical Ionization ◽  
Negative Ions ◽  
Ion Concentration ◽  
Oxidation States ◽  
Metallic Ions ◽  
Ion Chemistry ◽  
Hydrocarbon Flames

A pair of laminar, premixed, CH4–O2 flames above 2000 K at atmospheric pressure, one fuel-rich (FR) and the other fuel-lean (FL), were doped with ~10−6 mol fraction of the second-row transition metals Y, Zr, Nb, and Mo. Since these hydrocarbon flames contain natural ionization, metallic ions were produced in the flames by the chemical ionization (CI) of metallic neutral species, primarily by H3O+ and OH− as CI sources. Both positive and negative ions of the metals were observed as profiles of ion concentration versus distance along the flame axis by sampling the flames through a nozzle into a mass spectrometer. For yttrium, the observed ions include the YO+•nH2O (n = 0–3) series, and Y(OH)4−. With zirconium, they include the ZrO(OH)+•nH2O (n = 0–2) series, and ZrO(OH)3−. Those observed with niobium were the cations Nb(OH)3+ and Nb(OH)4+, and the single anion NbO2(OH)2−. For molybdenum, they include the cations MoO(OH)2+ and MoO(OH)3+, and the anions MoO3− and MoO3(OH)−. Not every ion was observed in each flame; the FL flame tended to favour the ions in higher oxidation states. Also, flame ions in higher oxidation states were emphasized for these second-row transition metals compared with their first-row counterparts. Some ions written as members of hydrate series may have structures different from those of simple hydrates; e.g., YO+•H2O = Y(OH)2+ and ZrO(OH)+•H2O = Zr(OH)3+, etc. The ion chemistry for the production of these ions by CI in flames is discussed in detail. Keywords: transition metals, ions, flame, gas phase, negative ions.

Frontiers in the infrared spectroscopy of gas phase metal ion complexes

2005 ◽  
Vol 29 (12) ◽  
pp. 1495 ◽  
Author(s):  
Nicholas R. Walker ◽  
Richard S. Walters ◽  
Michael A. Duncan
Keyword(s):  
Infrared Spectroscopy ◽  
Gas Phase ◽  
Metal Ion ◽  
Metal Ion Complexes

Serine–Ca2+ versus serine–Cu2+ complexes — A theoretical perspective

2010 ◽  
Vol 88 (8) ◽  
pp. 759-768 ◽  
Author(s):  
Al Mokhtar Lamsabhi ◽  
Otilia Mó ◽  
Manuel Yáñez
Keyword(s):  
Gas Phase ◽  
Electron Density ◽  
Potential Energy Surfaces ◽  
Metal Ion ◽  
Theoretical Perspective ◽  
Binding Energies ◽  
Interacting Systems ◽  
Intramolecular Hydrogen ◽  
Energy Surfaces ◽  
Doubly Charged

The association of Ca2+ and Cu2+ to serine was investigated by means of B3LYP DFT calculations. The [serine–M]2+ (M = Ca, Cu) potential energy surfaces include, as does the neutral serine, a large number of conformers, in which a drastic reorganization of the electron density of the serine moiety is observed. This leads to significant changes in the number and strength of the intramolecular hydrogen bonds existing in the neutral serine tautomers. In some cases, a proton is transferred from the carboxylic OH group to the amino group and accordingly, some of the more stable [serine–M]2+ complexes can be viewed as the result of the interaction of the zwiterionic form of serine with the doubly charged metal ion. Whereas the interaction between Ca2+ and serine is essentially electrostatic, that between Cu2+ and serine has a non-negligible covalent character, reflected in larger electron densities at the bond critical points between the metal and the base, in the negative values of the electron density between the two interacting systems, and in much larger Cu2+ than Ca2+ binding energies. More importantly, the interaction with Cu2+ is followed by a partial oxidation of the base, which is not observed when the metal ion is Ca2+. The main consequence is that in Cu2+ complexes a significant acidity enhancement of the serine moiety takes place, which strongly favors the deprotonation of the [serine–Cu]2+ complexes. This is not the case for Ca2+ complexes. Thus, [serine–Ca]2+ complexes, like those formed by urea, thiourea, selenourea, or glycine, should be detected in the gas phase. Conversely, the complexes with Cu2+ should deprotonate spontaneously and therefore only [(serine–H)–Cu]+ monocations should be experimentally accessible.

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