摘要：

Three-coordinate 1 1 and 1 2 compounds of copper(i) halides with tricyclohexylphosphine have been synthesised and characterized by single crystal X-ray structure determinations,63Cu NQR spectroscopy, solid state31P CPMAS NMR spectroscopy, and low frequency vibrational spectroscopy. The 1 1 compounds crystallize as isomorphous, centrosymmetric [(PCy3)Cu(μ-X)2Cu(PCy3)] dimers with three-coordinate (PCuX2) copper. Solid state31P CPMAS NMR spectra show asymmetric quartets with the spectra of the chloride and bromide compounds broadened by quadrupole relaxation effects. For X I,1J(31P–63Cu) is 1.74 kHz with the quadrupole distortion parameter,dνCu, 11.5 × 109Hz2. Far infrared spectra of the compounds are unusually complex with groups of strong bands in the region expected forν(CuX) vibrational modes (100–260 cm1). The 1 2 compounds crystallize as [CuX(PCy3)2] monomers. The solid state31P NMR spectra of the bromide and iodide compounds show sharp asymmetric quartets with1J(P–Cu) 1.20 and 1.23 kHz anddνCu8.7 and 10.3 × 109Hz2respectively. Relaxation effects collapse the spectrum of the chloride to a broad doublet. Room temperature63Cu NQR frequencies for [CuX(PCy3)2] are found to be 34.5, 33.43 and 32.06 MHz for X Cl, Br and I respectively and are of the order of 4 MHz greater than values recorded for the 1 1 complexes. Far infrared spectra of the complexes exhibit strong bands due toν(CuX) vibrational modes at 253, 189 and 156 cm1for X Cl, Br and I.

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