Structural and solid state 31P NMR studies of the four-coordinate copper(I) complexes [Cu(PPh3)3X] and [Cu(PPh3)3(CH3CN)]X

J.V. Hanna, S.E. Boyd, P.C. Healy, G.A. Bowmaker, Brian Skelton, Allan White

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28 Citations (Scopus)


The tris(triphenylphosphine) copper(I) complexes [(PPh3)(3)CuX] for X = Cl (1), Br (2), I (3), ClO4 (4), BF4 (5), [(PPh3)(3)CuCl]center dot CH3CN (1a), [Cu(PPh3)(3)(CH3CN)]X for X = ClO4 (6), BF4 (7), and [Cu(PPh3)(3)(CH3CN)]X center dot CH3CN for X = SiF5 (8), PF6 (9) have been studied by solid state P-31 CP/MAS NMR spectroscopy together with single crystal X-ray diffraction for compounds (6)-(9), the latter completing the availability of crystal structure data for the series. Compounds (1) -(5) form an isomorphous series in space group P3 (a similar to 19, c similar to 11 angstrom) with three independent molecules in the unit cell, all disposed about 3-fold symmetry axes. Average values (with estimated standard deviations) for the P-Cu-P, P-Cu-X bond angles and Cu-P bond lengths in compounds (1)-(3) are 110.1(6)degrees, 108.8(6)degrees and 2.354(8) angstrom and 115.2(6)degrees, 102.8(9)degrees and 2.306(9) angstrom for compounds (4) and (5). For the acetonitrile solvated compound (1a), the corresponding parameters are 115(4)degrees, 103(3)degrees and 2.309(3) angstrom. The solid state P-31 CP/MAS NMR quadrupole distortion parameters, dv(Cu), for (1)-(3) and (1a) are all less than 1 x 10(9) Hz(2), despite the changes in donor properties of the halide in (1) -(3), and the coordination geometry of the P3CuX core in (1a). Change of anion to ClO4- and BF4- in compounds (4) and (5) results in a significant increase of dv(Cu) to 4.4-5.2 10(9) Hz(2) and 5.2-6.0 x 10(9) Hz(2), respectively. Compounds (6) and (7) crystallise as isomorphous [Cu(PPh3)(3)(CH3CN)]X salts in space group Pbca, (a similar to 17.6, b similar to 22.3, c similar to 24.2 angstrom), while compounds (8) and (9) crystallize as isomorphous acetonitrile solvated salts [Cu(PPh3)(3)(CH3CN)]X center dot CH3CN in space group P (1) over bar1 (a similar to 10.5, b similar to 13.0, c similar to 19.5 angstrom, a similar to 104, beta similar to 104, gamma similar to 94 degrees). The P3CuN angular geometries in all four compounds are distorted from tetrahedral symmetry with average P-Cu-P, P-Cu-N angles and Cu-P bond lengths of 115(4)degrees, 103(4)degrees and 2.32(1) angstrom, with dv(Cu) ranging between 1.3 and 2.5 x 10(9) Hz(2). The solid state Si-29 CP/MAS NMR spectrum of the pentafluorosilicate anion in compound (8) is also reported, affording (1)J(Si-29, F-19) = 146 Hz.
Original languageEnglish
Pages (from-to)2547-2556
JournalDalton Transactions
Issue number15
Publication statusPublished - 2005


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