TY - JOUR
T1 - Preparation of Copper Organometallics via Nucleophilic Substitution of CpCuPPh3
T2 - Syntheses and X-ray Structure Determinations of [Li(THF)4]+[(fluorenyl)2CuPPh3]- and [Cy3PCu(μ-C≡CtBu)2Cu(PPh3)2] (THF = Tetrahydrofuran, Fluorenyl = C13H9)
AU - Edwards, Andrew J.
AU - Paver, Michael A.
AU - Raithby, Paul R.
AU - Rennie, Moira Ann
AU - Russell, Christopher A.
AU - Wright, Dominic S.
PY - 1994/12/1
Y1 - 1994/12/1
N2 - The ion-separated complex [Li(THF)4]+[(fluorenyl)2CuPPh3]- (2) and the dinuclear complex [Cy3PCu(μ-C≡CtBu)2Cu(PPh3)2] (3) have been synthesized by nucleophilic substitution of CpCuPPh3 (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, 1H and 31P 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) Å, b = 15.230(3) Å, c = 20.050(4) Å, β = 105.03(3)°, V = 11037(4) Å3, 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 P1, with cell dimensions a = 13.185(3) Å, b = 13.572(3) Å, c = 22.516(5) Å, α = 83.97(3)°, β = 77.12(3)°, γ = 66.08(3)°, V = 3590.0(14) Å3, 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) Å. The preparation of complexes 2 and 3 demonstrates the potential of 1 as a starting point for the halide-free syntheses of copper organometallics.
AB - The ion-separated complex [Li(THF)4]+[(fluorenyl)2CuPPh3]- (2) and the dinuclear complex [Cy3PCu(μ-C≡CtBu)2Cu(PPh3)2] (3) have been synthesized by nucleophilic substitution of CpCuPPh3 (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, 1H and 31P 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) Å, b = 15.230(3) Å, c = 20.050(4) Å, β = 105.03(3)°, V = 11037(4) Å3, 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 P1, with cell dimensions a = 13.185(3) Å, b = 13.572(3) Å, c = 22.516(5) Å, α = 83.97(3)°, β = 77.12(3)°, γ = 66.08(3)°, V = 3590.0(14) Å3, 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) Å. The preparation of complexes 2 and 3 demonstrates the potential of 1 as a starting point for the halide-free syntheses of copper organometallics.
UR - http://www.scopus.com/inward/record.url?scp=0000381858&partnerID=8YFLogxK
U2 - 10.1021/om00024a045
DO - 10.1021/om00024a045
M3 - Article
AN - SCOPUS:0000381858
SN - 0276-7333
VL - 13
SP - 4967
EP - 4972
JO - Organometallics
JF - Organometallics
IS - 12
ER -