PREPARATION OF COPPER ORGANOMETALLICS VIA NUCLEOPHILIC-SUBSTITUTION OF CPCUPPH(3) - SYNTHESES AND X-RAY STRUCTURE DETERMINATIONS OF [LI(THF)(4)](+)[(FLUORENYL)(2)CUPPH(3)](-) AND [CY(3)PCU(MU-C-C(T)BU)(2)CU(PPH(3))(2)] (THF=TETRAHYDROFURAN, FLUORENYL=C13H9)

The ion-separated complex [Li(THF)(4)](+)[(fluorenyl)(2)CuPPh(3)](-)(2) and the dinuclear complex [Cy(3)PCu(mu-C=C(t)Bu)(2)Cu(PPh(3))(2)] (3) have been synthesized by nucleophilic substitution of CpCuPPh(3) (1) with fluorenyllithium (1:1 or 1:2 equiv) and with tert-butylacetylide lithium and tricyclohexylphosphine (1:1:1 equiv), respectively. Both complexes have been characterized by elemental analyses, solid-state IR spectroscopy, H-1 and (31)p NMR spectroscopy, and low-temperature X-ray diffraction studies. Complex 2 crystallizes in the monoclinic space group C2/c, with cell dimensions a = 37.425(7) Angstrom, b = 15.230(3) Angstrom, c = 20.050(4) Angstrom, beta = 105.03(3)degrees, V = 11037(4) Angstrom(3), and Z = 8. The distorted trigonal planar copper anion of complex 2 is the first example of a mononuclear cuprate stabilized by neutral phosphine coordination. Complex 3 crystallizes in the triclinic space group P $($) over bar$$ 1, with cell dimensions a = 13.185(3) Angstrom, b = 13.572(3) Angstrom, c = 22.516(5) Angstrom, alpha = 83.97(3)degrees, beta = 77.12(3)degrees, gamma = 66.08(3)degrees, V = 3590.0(14) Angstrom(3), and Z = 2. Complex 3 is an unusual binuclear complex containing both distorted three and four coordinate copper centers bridged by acetylide ligands. It contains an extremely short Cu...Cu distance of 2.389(1) Angstrom. The preparation of complexes 2 and 3 demonstrates the potential of 1 as a starting point for the halide-free syntheses of copper organometallics.