Issue 13, 2002

Structural and spectroscopic studies on three-coordinate complexes of copper(i) halides with tricyclohexylphosphine

Abstract

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 state 31P 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 state 31P 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 × 109 Hz2. Far infrared spectra of the compounds are unusually complex with groups of strong bands in the region expected for ν(CuX) vibrational modes (100–260 cm−1). The 1 ∶ 2 compounds crystallize as [CuX(PCy3)2] monomers. The solid state 31P NMR spectra of the bromide and iodide compounds show sharp asymmetric quartets with 1J(P–Cu) 1.20 and 1.23 kHz and dνCu 8.7 and 10.3 × 109 Hz2 respectively. Relaxation effects collapse the spectrum of the chloride to a broad doublet. Room temperature 63Cu 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 to ν(CuX) vibrational modes at 253, 189 and 156 cm−1 for X = Cl, Br and I.

Graphical abstract: Structural and spectroscopic studies on three-coordinate complexes of copper(i) halides with tricyclohexylphosphine

Supplementary files

Article information

Article type
Paper
Submitted
05 Dec 2001
Accepted
22 Apr 2002
First published
17 May 2002

J. Chem. Soc., Dalton Trans., 2002, 2722-2730

Structural and spectroscopic studies on three-coordinate complexes of copper(I) halides with tricyclohexylphosphine

G. A. Bowmaker, S. E. Boyd, J. V. Hanna, R. D. Hart, P. C. Healy, B. W. Skelton and A. H. White, J. Chem. Soc., Dalton Trans., 2002, 2722 DOI: 10.1039/B111121N

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