
TY  - JOUR
A1  - Bowmaker, Graham A. 
A1  - Effendy, 
A1  - Hart, Robert D. 
A1  - Kildea, John D. 
A1  - Skelton, Brian W. 
A1  - Silva, Eban N. de 
A1  - White, Allan H. 
T1  - Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXIV Syntheses, Spectroscopy and Structures of Some 1 : 4 Adducts of Copper(I) and Silver(I) Perchlorates with Triphenylarsine and Triphenylstibine
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1997
VL  - 50
IS  - 6
SP  - 539
EP  - 552
KW  - 
UR  - https://doi.org/10.1071/C96031 
N2  - Syntheses and room-temperature single crystal X-ray structure determinations are recorded for adducts &#91;M(EPh3)4&#93; (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 &#x2248; 14&#183;4, c &#x2248; 52 &#197;, hexagonal setting) with the metal and chlorine atoms located on crystallographic threefold axes. In these arrays Cu&#8211;E (axial, off axis) are 2&#183;493(2), 2&#183;533(1) for (1), and 2&#183;572(1), 2&#183;577(1) &#197; 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&#183;652(3), 2&#183;680(2) in (3); 2&#183;732(2), 2&#183;7295(8) &#197; 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: &#91;Ag(SbPh3)4&#93; (NO3) (5) is of the rhombohedral family with no cation core disorder, Ag&#8211;E (axial, off axis) being 2&#183;720(4), 2&#183;725(2) &#197;, while the structural characterization of a 1 : 4 triphenylarsine adduct of silver nitrate is recorded as its tetraethanol solvate, namely &#91;Ag(AsPh3)4&#93; (NO3).~ 4C2H5OH(6), monoclinic, C2/c, a 18&#183;373(4), b 20&#183;786(5), c 21&#183;070(8) &#197;, &#946; 108&#183;18(3)&#176;, Z = 4 f.u. The silver atom of the &#91;Ag(AsPh3)4&#93;+cation unusually lies on a crystallographic 2 (rather than a 3 ) axis of the incipiently23 (T) array, with Ag-As 2&#183;649(2), 2&#183;650(2) &#197; and As-Ag-As ranging from 108&#183;22(4) to 111&#183;41(6)&#176;. 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 &#91;Ag(PPh3)4&#93;2 (SiF6).py (7). Bands in the far-infrared spectra of &#91;M(AsPh3)4&#93; (ClO4) are assigned to v(MAs) vibrations at 119 (M = Cu) and 103 cm&#175;1 (M = Ag); this produces a more consistent picture of the variation in the wavenumbers of the v(ME) modes in &#91;M(EPh3)4&#93;+ compounds than was available previously. 
ER  -

