CHEMISTRY OF COPPER(I) BETA-DIKETONATE COMPLEXES .6. SYNTHESIS, CHARACTERIZATION AND CHEMICAL-VAPOR DEPOSITION OF DIMETHYL-6,6,7,7,8,8,8-HEPTAFLUORO-3,5-OCTANEDIONE (FOD), COPPER(I)L COMPLEXES AND THE SOLID-STATE STRUCTURE OF (FOD)CU(PME3)

A series of copper(I) compounds of the general formula (fod)CuL, where fod = imethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione, and L = PMe3 , PEt3, 1,5-cyclooctadiene (1,5-COD), vinyltrimethylsilane (VTMS), 2-b utyne, bis(trimethylsilyl)acetylene (BTMSA), have been prepared by the reaction of Na[fod] with CuCl in the presence of the appropriate amou nt of the Lewis base, L. All the compounds were characterized by eleme ntal analysis, H-1, C-13, F-19, P-31 and IR spectroscopies. The spectr oscopic data are consistent with the chelation of the beta-diketonate ligand through its oxygen atoms to the copper(I) center. The analytica l data are consistent with the empirical formula (fod)CuL. One compoun d, (fod)CuPMe3, was characterized in the solid-state by single-crystal X-ray diffraction which confirmed the empirical formula and revealed the monomeric nature of this species in the solid state. The distorted trigonal planar coordination environment observed for this species is common to these species. The Cu-0 distances are significantly differe nt within the limits of error on the data possibly as a result of indu ctive effects of the different beta-diketonate substituents. Crystal d ata: Triclinic space group P1BAR, a = 10.052(2) angstrom, b = 11.871(2 ) angstrom, c = 16287(3) angstrom, alpha = 109.84(1)-degrees, beta = 9 2.18(2)-degrees, gamma = 90.34(2)-degrees, V = 1826.5(6) angstrom3, Z = 4, R(w) = 7.09% and R(wF) = 7.28%. Hot- and cold-wall chemical vapor deposition experiments revealed that these species are generally not suitable as precursors for the deposition of copper due to their low t her-mal stability. While pure copper films could be deposited, as dete rmined by Auger electron spectroscopy, from the compounds (fod)CuL, wh ere L = PMe3, 2-butyne and BTMSA, heating the precursors to increase t heir vapor pressures resulted in significant thermal decomposition in the source reservoir. As a result, deposition rates of only 100 angstr om/min were achieved. No selectivity was observed on W versus SiO2 sub strates under the conditions employed. The other compounds, (fod)CuL, where L = 1,5-COD, VTMS, were too thermally unstable for CVD experimen ts.