Synthesis and Characterization of (.beta.-Diketonate)(7-tert-butoxynorbornadiene)copper(I) Compounds, a Series of New Copper CVD Precursors

Organocopper compounds of the general formula (B-diketonate)Cu('I-t-BuO-NBD) where 7-t-BuO-NBD = 7-tert-butoxynorbornadiene and B-diketonate = 1,1,1,5,5,5-hexafluoro-2,4pentanedionate (l), l,l,l-trifluoro-2,4-pentanedionate (21, 2,4-pentanedionate (31, 4,4,4trifluoro-l-(2-thienyl)-l,3-butanedionate (4), 4,4,4-trifluoro-l-phenyl-1,3-butanedionate (5)) and 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,S-octanedionate (6) were prepared by reaction of CuCl with Na(B-diketonate) in the presence of 7-t-BuO-NBD. All compounds were characterized by elemental analyses and lH, 13C, and 19F NMR, IR, and mass spectra. Singlecrystal structures of compounds 1,4, and 5 were determined by X-ray diffraction analyses that showed mononuclear copper species with coordination of a chelating P-diketonate ligand through two oxygen atoms and the 7-t-BuO-NBD through one C-C double bond and an oxygen atom in the solid state. Variable-temperature 'H NMR spectral data of compound 2 in the solution are consistent with this structural nature. Hot-wall chemical vapor deposition experiments revealed that compound 1 is suitable as a precursor to deposit copper films in the temperature range 200-260 "C. Crystallographic data for compounds 1,4, and 5: (hfac)Cu(7-t-BuO-NBD) (1) crystallizes in monoclinic system, space group P21/c, a = 8.9230) A, b = 19.558(4) A, c = 10.495(3) A, p = 90.45(2)", V = 1831.3(7) A3, 2 = 4. (Ttfac)Cu(7-t-BuO-NBD) (4) crystallizes in monoclinic system, space group P21/n, a = 10.689(6) A, b = 9.712(4) A, c = 19.323(4) A, P = 97.22(3)", V = 1990.2(15) Hi3, 2 = 4. (Btfac)Cu(7-tBuO-NBD) (5) crystallizes in triclinic system, space group Pi, a = 9.6170) A, b = 9.894(4) A, c = 11.322(2) A, a = 104.57(2)", /3 = 95.50(1)", y = 104.76(3)", V = 993.4(5) A3, 2 = 2.