ETD

Archivio digitale delle tesi discusse presso l'Università di Pisa

Tesi etd-05022007-095352


Tipo di tesi
Tesi di dottorato di ricerca
Autore
Peloso, Riccardo
Indirizzo email
riccardo@dcci.unipi.it
URN
etd-05022007-095352
Titolo
SYNTHESIS, CHARACTERIZATION AND CO / OLEFIN EXCHANGE REACTION OF COPPER(I) DERIVATIVES CONTAINING BIDENTATE OXYGEN- AND NITROGEN LIGANDS
Settore scientifico disciplinare
CHIM/03
Corso di studi
SCIENZE CHIMICHE
Relatori
Relatore Prof. Pampaloni, Guido
Parole chiave
  • copper(I) olefin compounds
  • copper(I) carbonyls
  • copper(I)
  • CO/olefin exchange
  • bis(pyrazolyl)methane
  • bis(pyrazolyl)borate
  • fluorinated ligands
Data inizio appello
15/02/2007
Consultabilità
Non consultabile
Data di rilascio
15/02/2047
Riassunto
A large number of olefin- and carbonyl derivatives of copper(I) have been synthesized and characterized and their CO/olefin exchange reactions have been studied. Trifluoroacetate, hexafluoroacetylacetonate, bis[3,5-(trifluoromethyl)pyrazolyl)borate, and several bis(pyrazolyl)methanes have been employed as ancillary ligands. IR- and NMR spectra of complexes are extensively discussed. Particular emphasis has been laid on the trends observed in the IR spectra of carbonyl compounds with respect to the variations of the ancillary ligand. Similarly, 1H NMR spectra of olefin derivatives have been examined and chemical shift changes due to coordination for vinyl hydrogen- and carbon nuclei have been highlighted. The carbonylation reactions of Cu(CF3COO)(olefin), Cu(hfacac)(olefin), Cu[BH2(3,5-(CF3)2Pz)2](olefin), and [Cu{CH2(3,5-Me2Pz)2}(olefin)](OTf) have been studied by gas volumetric methods and enthalpy- and entropy changes have been obtained from experiments at variable temperature. These data for copper(I) are compared with those obtained for other transition metal systems such as VCp2(CO) and AuCl(CO).
File