99527-34-1Relevant articles and documents
Lewis-base adducts of group 11 metal(I) compounds. LXIV: Syntheses, spectroscopy structures of some 1:4 adducts of copper(I) and silver(I) perchlorates with triphenylarsine and triphenylstibine
Bowmaker, Graham A.,Effendy,Hart, Robert D.,Kildea, John D.,De Silva, Eban N.,Skelton, Brian W.,White, Allan H.
, p. 539 - 552 (2007/10/03)
Syntheses and room-temperature single crystal X-ray structure determinations are recorded for adducts [M(EPh3)4] (ClO4), M = Cu, E = As (1), Sb (2); M = Ag, E = As (3), Sb (4), enabling comparison with analogous, previously studied MP4 and MN4 environments. The four complexes so characterized all crystallize in the familiar rhombohedral R 3 array (a ≈ 14·4, c ≈ 52 A, hexagonal setting) with the metal and chlorine atoms located on crystallographic threefold axes. In these arrays Cu-E (axial, off axis) are 2·493(2), 2·533(1) for (1), and 2·572(1), 2·577(1) A for (2), the disparity in the two independent M-E distances being diminished relative to those of previously studied phosphorus analogues, perhaps in consequence of increasing E size. In (3) and (4), some cation disorder is evident in respect of the ligand pnictide atom (E); for the major components Ag-E are 2·652(3), 2·680(2) in (3); 2·732(2), 2·7295(8) A in (4). Problems associated in defining the metal atom environment geometries in the latter are, nevertheless, more satisfactorily overcome in two further determinations of nitrate salts: [Ag(SbPh3)4] (NO3) (5) is of the rhombohedral family with no cation core disorder, Ag-E (axial, off axis) being 2·720(4), 2·725(2) A, while the structural characterization of a 1:4 triphenylarsine adduct of silver nitrate is recorded as its tetraethanol solvate, namely [Ag(AsPh3)4] (NO3).～4C2H5OH (6), monoclinic, C 2/c, a 18·373(4), b 20·786(5), c 21·070(8) A, β 108·18(3)°, Z = 4 f.u. The silver atom of the [Ag(AsPh3)4]+ cation unusually lies on a crystallographic 2 (rather than a 3) axis of the incipiently 23 (T) array, with Ag-As 2·649(2), 2·650(2) A and As-Ag-As ranging from 108·22(4) to 111·41(6)°. The structure determination of a chloroform solvate of (2), denoted (2a), of low precision, is noted, together with the structure of an interesting artefact, isomorphous with the rhombohedral oxoanion array, modelled as [Ag(PPh3)4]2 (SiF6).py (7). Bands in the far-infrared spectra of [M(AsPh3)4] (ClO4) are assigned to ν(MAs) vibrations at 119 (M = Cu) and 103 cm-1 (M = Ag); this produces a more consistent picture of the variation in the wavenumbers of the ν(ME) modes in [M(EPh3)4]+ compounds than was available previously.
