THE CHEMISTRY OF COPPER(I) BETA-DIKETONATE COMPOUNDS .4. SYNTHESES AND CHARACTERIZATION OF CUXLN (X=BETA-DIKETONATE OR CL, L=PME3, N=2 OR 4, L=PET3, N=2)

The salts [Cu(PMe3)4]+[CuCl2]- and [Cu(PMe3)4]+[beta-diketonate]-[beta-diketonate = 1,1,1,5,5,5-hexafluoroacetylacetonate (hfacac), 1,1,1-trifluoroacetylacetonate (tfacac) or acetylacetonate (acac)] were prepared by the displacement of the co-ordinating anions Cl- and beta-diketonate from the copper(I) complexes [CuX(PMe3)] (X = Cl or beta-diketonate) by addition of an excess of PMe3. These species were characterized by a variety of spectroscopic methods including P-31 NMR spectroscopy which revealed coupling between P-31 and Cu-63, Cu-65 in the cation. Two examples were characterized in the solid state by single-crystal X-ray diffraction: [Cu(PMe3)4]+ [CuCl2]-, space group P2(1)3, a = 13.584(1) angstrom and Z = 12; [Cu(PMe3)4]+[hfacac]-, space group Pmmn, a = 10.703(2), b = 15.077(3), c = 8.997(2) angstrom and Z = 2. The cations exhibit an approximately tetrahedral co-ordination environment and the anion [CuCl2]- is linear. The addition of excess of PEt3 to (CuX(PEt3)] resulted in formation of [CuX(PEt3)2] in contrast to the PMe3 analogues. The compound [CuCl(PEt3)2] was found to be monomeric in benzene solution by cryoscopic molecular weight determination and has high volatility.