RESUMO
Negatively charge-tagged N-heterocyclic carbenes have been formed in solution via deprotonation of imidazolium ions bearing acid side groups and transferred to the gas phase via ESI(-)-MS. The structure of the putative and apparently stable gaseous carbenes formed in such conditions were then probed via reactions with carbon dioxide using a triple quadrupole mass spectrometer particularly optimized for ion/molecule reactions of ESI-generated ions. Complete conversion to imidazolium carboxylates was achieved, which seems to demonstrate the efficiency of the transfer, the gas-phase stability, and the long-lived nature of these unprecedented charge-tagged carbenes and their predominance in the ionic population. Comprehensive studies on the intrinsic reactivity of N-heterocyclic carbenes with silent charge tags are therefore possible. Graphical Abstract á .
RESUMO
The use of a charge-tagged acrylate derivative bearing an imidazolium tag to study the Morita-Baylis-Hillman reaction via ESI-MS(/MS) monitoring and the effect of such tag (imidazolium cations and ion pairs) over TSs is described. The ionic nature of the substrate was meant to facilitate ESI transfer to the gas phase for direct mass spectrometric analysis. The detection and characterization of charged intermediates has suggested major reaction pathways. DFT calculations considering the effect of a polar and protic solvent (methanol), of a polar and aprotic solvent (acetonitrile), and of no solvent (gas phase) were used to predict possible TSs through a common accepted intermediate. The controversial proton transfer step, which may proceed via Aggarwal's or McQuade's proposals, was evaluated. Calculations predicted the formation of electrostatic intermediate complexes with both the cation and anion when charge-tagged reagents are used. These complexes contribute to the positive ionic liquid effect, and based on the formation of these unique complexes, a rationale for the ionic liquid effect is proposed. These complexes also pointed to a plausible explanation for the positive ionic liquid effect observed in several reactions that are difficult to be carried out in organic solvents but have shown a beneficial effect when performed in ionic liquids.
Assuntos
Acetonitrilas/química , Imidazóis/química , Indicadores e Reagentes/química , Líquidos Iônicos/química , Acrilatos , Catálise , Prótons , Solventes/química , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas em TandemRESUMO
We describe the synthesis of novel mononuclear and dinuclear copper complexes and an investigation of their behaviour in solution using mass spectrometry (ESI-MS and ESI-MS/MS) and in the solid state using X-ray crystallography. The complexes were synthesized from two widely used diacetylpryridine (dap) ligands, i.e. 2,6-diacetylpyridinebis(benzoic acid hydrazone) and 2,6-diacetylpyridinebis(2-aminobenzoic acid hydrazone). Theoretical calculations (DFT) were used to predict the complex geometries of these new structures, their equilibrium in solution and energies associated with the transformations.