Synthesis, characterization, crystal structures and computational studies on novel cyrhetrenyl hydrazones

Johana Gómez, Nelson Leiva, Rodrigo Arancibia, Juan Oyarzo, Gonzalo E. Buono-Core, A. Hugo Klahn, Vania Artigas, Mauricio Fuentealba, Ramon Bosque, Gabriel Aullón, Concepción López, Mercè Font-Bardía, Teresa Calvet

Research output: Contribution to journalArticlepeer-review

13 Scopus citations

Abstract

The synthesis of novel cyrhetrenyl hydrazones of general formula [Re{(η5-C5H4[Formula presented]1) = NNHR2}(CO)3] {with R1 = H and R2 = 4-NO2[Formula presented]6H4(4a), C6H5(4b) or H (4c) or R1 = Me and R2 = 4-NO2[Formula presented]6H4(5a), C6H5(5b) or H (5c)} is described. Compounds 4a–4c and 5a–5c were characterized by mass spectrometry and IR spectroscopy.1H and13C{1H} NMR studies revealed that 4a–4c and 5a–5c adopt the anti-(E) configuration in solution. X-ray crystal structures of compounds 4a and 5c confirmed the trans-arrangement of the cyrhetrenyl “Re(η5-C5H4)(CO)3” and the -NHR2moieties and the existence of strong hydrogen bonds involving the [Formula presented] unit. Molecular Orbital calculations at a DFT level have also been carried out in order to rationalize the influence of the nature of the substituent R3of [R3CH = NNH(4-NO2[Formula presented]6H4)] (R3 = ferrocenyl, (3a), cyrhetrenyl (4a), phenyl (6a) or cymantrenyl (7a) on the electronic delocalization, the nucleophilicity of the imine carbon, the polarizability and hyperpolarizability of these compounds, and computational studies using time-dependent density functional (TD-DFT) calculations have also been carried out in order to assign the bands detected in their electronic spectra and to explain the effect produced by the solvent.

Original languageEnglish
Pages (from-to)129-137
Number of pages9
JournalJournal of Organometallic Chemistry
Volume819
DOIs
StatePublished - 2016
Externally publishedYes

Keywords

  • Computational studies
  • Crystal structure
  • Cyrhetrenyl hydrazones
  • Ferrocenyl hydrazones
  • NMR

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