Sequential solvation of atomic transition-metal ions. The second solvent molecule can bind more strongly than the first

Marinelli, Peter J.; Squires, Robert R.

doi:10.1021/ja00193a052

Cited by 211 publications

(175 citation statements)

References 1 publication

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“…However, calculated structures for the stable, hydrated hydroxyuranyl complexes do not appear to support this (vide infra). It is worthwhile noting that the relative ordering of the rate constants mirrors earlier studies of hydrate thermodynamics for first row transition metal monocations M ϩ , which showed that the bond energy for the second water molecule was Ն that of the first [43][44][45][46][47][48]; since this trend was not observed for alkali metals, it was rationalized in terms of orbital rehybridization. Since orbital rehybridization is also significant in the uranyl system [41], measurement of bond energies for the three H 2 O molecules attached to (UO 2 OH) ϩ is needed, but cannot be accomplished using the present experimental setup.…”

Section: Resultssupporting

confidence: 69%

Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations

Chien

Anbalagan

Zandler

et al. 2004

J. Am. Soc. Mass Spectrom.

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The intrinsic hydration of three monopositive uranyl-anion complexes (UO 2 A) ϩ (where A ϭ acetate, nitrate, or hydroxide) was investigated using ion-trap mass spectrometry (IT-MS). The relative rates for the formation of the monohydrates [(UO 2 A)(H 2 O)] ϩ , with respect to the anion, followed the trend: Acetate Ն nitrate ӷ hydroxide. This finding was rationalized in terms of the donation of electron density by the strongly basic OH Ϫ to the uranyl metal center, thereby reducing the Lewis acidity of U and its propensity to react with incoming nucleophiles, viz., H 2 O. An alternative explanation is that the more complex acetate and nitrate anions provide increased degrees of freedom that could accommodate excess energy from the hydration reaction. The monohydrates also reacted with water, forming dihydrates and then trihydrates. , for which recent theoretical studies [5][6][7][8] have suggested that strong interactions between the cation and solvent molecules, with significant charge transfer, cause the solvating species to behave like equatorial ligands. Therefore, specific interaction with solvent is likely to influence the physico-chemical behavior of the uranyl ion and its complexes in the environment. Unfortunately, explicit control over the interactions of solvent and non-solvent ligands with the uranyl ion is difficult, which makes the study of species-dependent uranium behavior complicated. To gain a better understanding of the intrinsic interactions between different uranium species and solvent, we have turned to investigations of uranyl-anion complexes in the gas phase. Recent studies have shown that ion-trap mass spectrometry can be used to probe intrinsic metal and metal-complex chemistry by exposing metal species to reagent gases deliberately added to the ion trap [9 -20], or to adventitious H 2 O present in the He bath gas used to collisionally cool ions and improve trapping efficiency [21][22][23][24]. Further motivating the present study is the fact that ion traps will shortly be used to characterize actinide speciation in samples from radioactive waste disposal sites, and a concise understanding of actinide behavior will be critical for correctly interpreting environmental data [25].We recently demonstrated that electrospray ionization (ESI) and multiple stage tandem mass spectrometry (MS) can be used to generate and characterize "solvated", gas-phase complexes featuring the uranyl ion coordinated by hydroxide, nitrate or a series of alkoxides [26]. In the pilot study reported here, ESI was used to produce gas-phase ions from solutions containing uranyl nitrate or uranyl acetate in deionized H 2 O. The dominant species generated by ESI were those having

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Section: Resultssupporting

confidence: 69%

Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations

Chien

Anbalagan

Zandler

et al. 2004

J. Am. Soc. Mass Spectrom.

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“…A similar ordering is observed for the bond dissociation energies (BDEs) of a second water ligand, but particularly notable is that the second BDEs exceed the first BDEs in the case of Cu and Au. This phenomenon was first discovered by Marinelli and Squires in an experimental study of M(H 2 O) n + cations of 3d metals [21] and attributed to the reorganization energy which is necessary to disturb the electron configuration of the metal ion upon approach of the first ligand, whereas the second ligand enters an already disturbed arrangement [22,23]. In other words, the first ligand already pays the bill of the second [24].…”

Section: Hydrated Coinage-metal Ionsmentioning

confidence: 90%

Theory meets experiment: Gas-phase chemistry of coinage metals

Roithová

Schröder

2009

Coordination Chemistry Reviews

101

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“…It is well known that Cu + forms very strongly bonded dicoordinated linear complexes and that the first two bond energies Cu + L and LCu + L are approximately equal and much higher than those with additional ligands as mentioned above [7][8][9][10][11][12][13][14][15]. Indeed, recent experimental data for H 2 O, NH 3 , (Me) 2 O, MeCN, and acetone indicate that the second binding energy is identical to the first one [7][8][9][10].…”

Section: Comparison Of Binding Energies Of Cu + Between the First Andmentioning

confidence: 96%

“…In these studies, the L 2 Cu + complexes rather than LCu + were choosen owing to experimental convenience. Since the first two bond energies Cu + L and CuL + L are approximately equal and much higher than those observed with additional ligands [7][8][9][10][11][12][13][14][15], the special stability of L 2 Cu + enables the measurements of the exchange equilibria. Although these results may provide somewhat restricted information, they are very valuable because they deal with the first two strongest bonding interactions.…”

Section: Introductionmentioning

confidence: 99%

Experimental and theoretical studies of the binding interaction between copper(I) cation and the carbonyl group

Than

Maeda

Irie

et al. 2007

International Journal of Mass Spectrometry

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Sequential solvation of atomic transition-metal ions. The second solvent molecule can bind more strongly than the first

Cited by 211 publications

References 1 publication

Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations

Intrinsic hydration of monopositive uranyl hydroxide, nitrate, and acetate cations

Theory meets experiment: Gas-phase chemistry of coinage metals

Experimental and theoretical studies of the binding interaction between copper(I) cation and the carbonyl group

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