SYNTHESIS, CHARACTERIZATION AND CO / OLEFIN EXCHANGE REACTION OF COPPER(I) DERIVATIVES CONTAINING BIDENTATE OXYGEN- AND NITROGEN LIGANDS

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).