Gas-Phase Reactions Between Thiourea and Ca<sup>2+</sup> : New Evidence for the Formation of [Ca(NH<sub>3</sub>)]<sup>2+</sup> and Other Doubly-Charged Species - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue ChemPhysChem Année : 2007

Gas-Phase Reactions Between Thiourea and Ca2+ : New Evidence for the Formation of [Ca(NH3)]2+ and Other Doubly-Charged Species

Résumé

The gas-phase reactions between Ca2+ and thiourea are investigated by means of electrospray ionization/mass spectrometry experiments. The MS/MS spectra of [Ca(thiourea)]2+ complexes show the appearance of new doubly charged species formed by the loss of NH3 and HNCS. Other intense peaks at m/z 43, 56, 60, 73, 76 and 98 are also observed, and assigned to monocations produced in different coulomb-explosion processes. The structures and bonding characteristics of the different stationary points of the [Ca(thiourea)]2+ potential energy surface (PES) were theoretically studied by DFT calculations carried out at B3LYP/cc-pWCVTZ level. The analysis of the topology of this PES permits to propose different mechanisms for the loss of ammonia and HNCS, and to identify, the m/z 43, 56, 60, 73, 76 and 98 peaks as H2NCNH+, CaNH2+, H2NCS+, CaSH+, thiourea+ and CaNCS+ ions respectively. There are significant dissimilarities between the reactivity of urea and thiourea, which are related to the lower ionization energy of the latter, and to the fact that thioenols are intrinsically more stable than enols with respect to the corresponding keto forms.
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hal-00162242 , version 1 (08-10-2018)

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Cristina Trujillo, Otilia Mó, Manuel Yáñez, Jean-Yves Salpin, Jeanine Tortajada. Gas-Phase Reactions Between Thiourea and Ca2+ : New Evidence for the Formation of [Ca(NH3)]2+ and Other Doubly-Charged Species. ChemPhysChem, 2007, 8 (9), pp.1330-1337. ⟨10.1002/cphc.200700113⟩. ⟨hal-00162242⟩

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