Lewis-base adducts of Group 11 metal(I) compounds .64. Syntheses, spectroscopy and structures of some 1:4 adducts of copper(I) and silver(I) perchlorates with triphenylarsine and triphenylstibine

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)over bar> array (a approximate to 14.4, c approximate to 52 Angstrom, 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) Angstrom 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) Angstrom 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) Angstrom, while the structural characterization of a 1:4 triphenylarsine adduct of silver nitrate is recorded as its tetraethanol solvate, namely [Ag(AsPh3)(4)](NO3).similar to 4C(2)H(5)OH (6), monoclinic, C2/c, a 18.373(4), b 20.786(5), c 21.070(8) Angstrom, beta 108.18(3)degrees, Z = 4f.u. The silver atom of the [Ag(AsPh3)(4)](+) cation unusually lies on a crystallographic 4? (rather than a 3) axis of the incipiently 23 (T) array, with Ag-As 2.649(2), 2.650(2) Angstrom and As-Ag-As ranging from 108.22(4) to 111.41(6)degrees. 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 v(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 v(ME) modes in [M(EPh3)(4)](+) compounds than was available previously.