Gas‐Phase Chemistry of Organocopper Compounds

Lamsabhi, Al Mokhtar; Yáñez, Manuel; Salpin, Jean‐Yves; Tortajada, Jeanine

doi:10.1002/9780470682531.pat0440

Cited by 9 publications

(12 citation statements)

References 245 publications

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“…For example, copper has the capacity to interact with nucleic acids, [2][3][4] and it shows a rather high affinity for DNA relative to that of other divalent metals. [5,6] Lead is another metal for which its toxicity is well known and its health damages are well established. Different reports have shown that the toxicity of this metal is partly due to its interaction with nucleic acids.…”

Section: Introductionmentioning

confidence: 99%

Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study

et al. 2014

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Gas-phase interactions between Pb(2+) ions and cytosine (C) were studied by combining tandem mass spectrometry, infrared multiple photon dissociation spectroscopy, and density functional theory (DFT) calculations. Both singly and doubly charged complexes were generated by electrospray. The [Pb(C)-H](+) complex was extensively studied, and this study shows that two structures, involving the interaction of the metal with the deprotonated canonical keto-amino tautomer of cytosine, are generated in the gas phase; the prominent structure is the bidentate form involving both the N1 and O2 electronegative centers. The DFT study also points out a significant charge transfer from the nucleobase to the low-lying p orbitals of the metal and a strong polarization of the base upon complexation. The various potential energy surfaces explored to account for the fragmentation observed are consistent with the high abundance of the [PbNH2](+) fragment ion.

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Section: Introductionmentioning

confidence: 99%

Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study

et al. 2014

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“…[15][16][17][18] It participates in different processes, such as enzyme regulation and stabilization of nucleic acids. While sites for calcium binding are implicit in these and other calcium-regulated processes, detailed characterization of such binding sites is very important.…”

Section: Introductionmentioning

confidence: 99%

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

2010

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The association of Ca 2+ and Cu 2+ 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 Ca 2+ and serine is essentially electrostatic, that between Cu 2+ 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 Cu 2+ than Ca 2+ binding energies. More importantly, the interaction with Cu 2+ is followed by a partial oxidation of the base, which is not observed when the metal ion is Ca 2+ . The main consequence is that in Cu 2+ 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 Ca 2+ 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 Cu 2+ should deprotonate spontaneously and therefore only [(serine-H)-Cu] + monocations should be experimentally accessible. Résumé :On étudié l'association des cations Ca 2+ et Cu 2+ avec la serine en utilisant la théorie de la fonctionnelle de la densité, B3LYP. Pour l'ion [sérine-M] 2+ (M = Ca, Cu), comme c'est le cas pour la sérine neutre, les surfaces d'énergie potentielle comportent un grand nombre de conformères dans lesquels on peut observer une réorganisation drastique de la densité électronique de la sérine. Ces changements conduisent à des changements significatifs dans le nombre et la force des liaisons hydrogènes intramoléculaires par rapport à celles qui existent dans les tautomères neutres de la sérine. Dans quelques cas, il se produit un transfert de proton du groupe OH de l'acide carboxylique vers le groupe amino et, en conséquence, un certain nombre des complexes les plus stables de l'ion [sérine-M] 2+ peuvent être considérés comme étant le résultat de l'interaction de la forme zwitterionique de la sérine avec l'ion métallique doublement chargé. Alors que l'interaction entre la Ca 2+ et la sérine est essentiellement électrostatique, celle entre le Cu 2+ et la sérine comporte un caractère covalent non négligeable qui est le reflet de densités électroniques plus grandes aux points critiques de liaison entre les deux systèmes en interaction ainsi que des énergies de liaisons beaucoup ...

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“…We conclude that the interaction between gold(I) and a H 2 O molecule in certain privileged complex structures is strong enough to warrant further theoretical and practical investigation. The latter, of course, is complicated by a variety of interactions in the condensed phase compared to the idealized and rather simple 1:1 association of isolated molecules described above . Certain interaction energies and bonding analysis results, nevertheless, remain valid, important and even dominant.…”

Section: Figurementioning

confidence: 97%

Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond

et al. 2015

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MP2 and DFT calculations with correlation consistent basis sets indicate that isolated linear anionic dialkylgold(I) complexes form moderately strong (ca. 10 kcal mol À1)A u···H hydrogen bonds with single H 2 Om olecules as donors in the absence of sterically demanding substituents. Relativistic effects are critically important in the attraction. Such bonds are significantly weaker in neutral, strong s-donor N-heterocyclic carbene (NHC) complexes (ca. 5kcal mol À1 ). The overall association (> 11 kcal mol À1 ), however,isstrengthened by co-operative,s ynergistic classical hydrogen bonding when the NHC ligands bear NH units.Further manipulation of the interaction by ligands positioned trans to the carbene,i s possible.

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Gas‐Phase Chemistry of Organocopper Compounds

Abstract: Introduction Performance of Different Theoretical Models Ligand‐Field Spectroscopy and Photofragmentation Processes Cu + and Cu 2+ Binding Energies Coordination Bonding Cu + … Show more

Cited by 9 publications

References 245 publications

Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study

Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study

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

Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond

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Gas‐Phase Chemistry of Organocopper Compounds

Abstract: Introduction Performance of Different Theoretical Models Ligand‐Field Spectroscopy and Photofragmentation Processes Cu + and Cu 2+ Binding Energies Coordination Bonding Cu + … Show more

Cited by 9 publications

References 245 publications

Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study

Gas‐Phase Interactions between Lead(II) Ions and Cytosine: Tandem Mass Spectrometry and Infrared Multiple‐Photon Dissociation Spectroscopy Study

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

Preparing Gold(I) for Interactions with Proton Donors: The Elusive [Au]⋅⋅⋅HO Hydrogen Bond

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