34010-81-6Relevant academic research and scientific papers
Structural and solid state31P NMR studies of the four-coordinate copper(I) complexes [Cu(PPh3)3X] and [Cu(PPh 3)3(CH3CN)]X
Hanna, John V.,Boyd, Sue E.,Healy, Peter C.,Bowmaker, Graham A.,Skelton, Brian W.,White, Allan H.
, p. 2547 - 2556 (2007/10/03)
The tris(triphenylphosphine)copper(I) complexes [(PPh3) 3CuX] for X = Cl (1), Br (2), I (3), ClO4 (4), BF 4 (5), [(PPh3)3CuCl]·CH3CN (1a), [Cu(PPh3)3(CH3CN)]X for X = ClO 4 (6), BF4 (7), and [Cu(PPh3) 3(CH3CN)]X·CH3CN for X = SiF5 (8), PF6 (9) have been studied by solid state 31P 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 ～ 19, c ～ 11 A) 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)°, 108.8(6)° and 2.354(8) A and 115.2(6)°, 102.8(9)° and 2.306(9) A for compounds (4) and (5). For the acetonitrile solvated compound (1a), the corresponding parameters are 115(4)°,103(3)° and 2.309(3) A. The solid state 31P CP/MAS NMR quadrupole distortion parameters, dvCu, for (1)-(3) and (1a) are all less than 1 × 109 Hz2, 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 ClO 4- and BF4- in compounds (4) and (5) results in a significant increase of dvCu to 4.4-5.2 109 Hz2 and 5.2-6.0 × 109 Hz2, respectively. Compounds (6) and (7) crystallise as isomorphous [Cu(PPh3) 3(CH3CN)]X salts in space group Pbca, (a ～ 17.6, b ～22.3, c ～24.2 A), while compounds (8) and (9) crystallize as isomorphous acetonitrile solvated salts [Cu(PPh3)3(CH 3CN)]X·CH3CN in space group P1 (a ～ 10.5, b ～ 13.0, c ～19.5 A, a ～ 104, β ～ 104, γ ～ 94°). 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)°, 103(4)° and 2.32(1) A, with dv Cu ranging between 1.3 and 2.5 × 109 Hz2. The solid state 29Si CP/MAS NMR spectrum of the pentafluorosilicate anion in compound (8) is also reported, affording 1J(29Si, 19F) = 146 Hz. The Royal Society of Chemistry 2005.
Lewis-Base Adducts of Group 11 Metal(I) Compounds. XXV Synthesis and Structural Properties of Tris(triphenylphosphine)copper(I) Perchlorate and Nitrate
Dyason, Jeffrey C.,Engelhardt, Lutz M.,Healy, Peter C.,Klich, Helen L.,White, Allan H.
, p. 2003 - 2012 (2007/10/02)
The compounds (PPh3)3CuOClO3 and (PPh3)3CuONO2 (as its mono-ethanol solvate) have been characterized by single-crystal structure analysis.Crystals of the perchlorate are trigonal, P3, a 18.748(8), c 11.731(6) Angstroem, Z 3, and are isomorphous with the chloride and tetrafluoroborate structures.R was 0.062 for N0 = 1452 independent observed reflections Cu-P distances are 2.314(5), 2.313(7) and 2.317(8) Angstroem for each of the three molecules in the unit cell, P-Cu-P angles are 114.5(3), 114.4(3) and 115.6(3) deg; Cu-O are 2.32(3), 2.23(3) and 2.23(3) Angstroem.Crystals of the nitrate are monoclinic, P21/n, a 14.875(5), b 23.349(7), c 14.141(7) Angstroem, β 91.73(3) deg, Z 4.R was 0.045 for No = 4066.Cu-P distances are 2.312(2), 2.337(2) and 2.339(2) Angstroem; P-Cu-P angles are 114.15(7), 121.37(6) and 113.42(6) deg.The nitrate group is monodentate with Cu-O, 2.174(4) Angstroem and Cu-O-N, 124.8(4) deg.
