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

Abstract

The tris(triphenylphosphine)copper(I) complexes [(PPh3)3CuX] for X = Cl (1), Br (2), I (3), ClO4 (4), BF4 (5), [(PPh3)3CuCl].CH3CN (1a), [Cu(PPh3)3(CH3CN)]X for X = ClO4 (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 approximately 19, c approximately 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) degrees, 108.8(6) degrees and 2.354(8)A and 115.2(6) degrees, 102.8(9) degrees and 2.306(9)A 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)A. The solid state 31P CP/MAS NMR quadrupole distortion parameters, dnu Cu, for (1)-(3) and (1a) are all less than 1 x 10(9) 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 ClO4- and BF4- in compounds (4) and (5) results in a significant increase of dnu Cu to 4.4-5.2 10(9) Hz2 and 5.2-6.0 x 10(9) Hz2, respectively. Compounds (6) and (7) crystallise as isomorphous [Cu(PPh3)3(CH3CN)]X salts in space group Pbca, (a approximately 17.6, b approximately 22.3, c approximately 24.2 A), while compounds (8) and (9) crystallize as isomorphous acetonitrile solvated salts [Cu(PPh3)3(CH3CN)]X.CH3CN in space group P1(a approximately 10.5, b approximately 13.0, c approximately 19.5 A, alpha approximately 104, beta approximately 104, gamma approximately 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)A, with dnu Cu ranging between 1.3 and 2.5 x 10(9) 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.

Synthesis and structural studies of a 1:2 adduct of silver(I) tetrakis(pyrazolyl)borate(III) with a tertiary phosphine

“…2 the connectivity between these P sites is established through the presence of this homonuclear 2 J( 31 P, 31 P) interaction, which shows the two resonances clearly resolved and correlated above and below the main diagonal. The observation of 2 J( 31 P, 31 P) from inequivalent P positions in solid bisand tris-Ag-phosphine and Cu-phosphine complexes has been previously well established [11][12][13][14][15]. The large chemical shift separation between the chemical shifts d 1 and d 2 , and the marked difference in the 1 J( 31 P, 107/109 Ag) measurements corroborates the very different bonding strengths exhibited by these PPh 3 moieties.…”

Transition‐Metal‐Induced Rearrangement of [(PhSn)4S6] Towards Ternary CuI/Sn/S or CuII/Sn/S Clusters

“…General : All synthetic steps, unless stated otherwise, were carried out under exclusion of oxygen and moisture by use of standard Schlenk procedures. [(PhSn) 4 S 6 ], [Cu(PPh 3 ) 3 Cl], and [Cu(PPh 3 ) 2 Cl 2 ] were prepared according to literature procedures. 1 H NMR and 13 C spectroscopy was carried out at 25 °C using a Bruker DRX 300 MHz spectrometer.…”

“…[(PhSn) 4 S 6 ], [14] [Cu(PPh 3 ) 3 Cl], [15] and [Cu(PPh 3 ) 2 Cl 2 ] [16] were prepared according to literature procedures. 1 HNMR and 13 Cs pectroscopy was carried out at 25 8Cu sing a Bruker DRX 300 MHz spectrometer.T he chemical shifts are given in ppm relative to the residual protons of deuterated solvent for 1 H and the solvent signal in 13 CNMR.…”

Bis(pyridine-κN)bis(triphenylphosphine-κP)copper(I) tetrafluoridoborate

“…For background literature on copper(I)-phosphine adducts, see: Hanna et al (1998Hanna et al ( , 2005. For isostructural [(PPh 3 ) 2 (py) 2 Cu][ClO 4 ], see: Engelhardt et al (1985) Experimental Crystal data [Cu(C 5…”