
%0 Journal Article
%A Bowmaker, Graham A. 
%A Effendy, 
%A Kildea, John D. 
%A Silva, Eban N. de 
%A White, Allan H. 
%T Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXI  Synthesis, Spectroscopy and Structural Systematics of Some 1 : 2 Binuclear Adducts of Silver(I) Compounds with Triphenylarsine, &#91;(Ph<emph tye="8">3</emph>As)<emph tye="8">2</emph>Ag(&micro;-X)<emph tye="8">2</emph>Ag(AsPh<emph tye="8">3</emph>)<emph tye="8">2</emph>&#93;, X &#61; Cl, Br, I, SCN
%J Australian Journal of Chemistry
%D 1997/08/19
%V 50
%N 6
%P 627-640
%K 
%R https://doi.org/10.1071/C96037
%U https://www.publish.csiro.au/paper/C96037 
%X The syntheses and room-temperature single-crystal X-ray structural characterization of binuclear 1 : 2 adducts formed between silver(I) (pseudo-)halides, AgX, and triphenylarsine, AsPh3, for X = Cl, Br, I, SCN (1)&#8211;(4), are described. The chloride (1), obtained from 2-methylpyridine, is triclinic, P-1, a 10&#183;410(2), b 12&#183;716(2), c 14&#183;196(6) &#197;, &#945; 113&#183;38(2), &#946; 109&#183;41(2), &#947; 75&#183;08(1)&#176;, Z = 1 (dimer); conventional R on F was 0&#183;037 for No 3979 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) reflections. The bromide (2a), obtained from 2,6-dimethylpyridine, and iodide (3), obtained from a mixture of AgI/saturated KI in MeOH solutions, are isomorphous, monoclinic, P 21/c a&#x2248; 24&#183;2, b &#x2248; 13&#183;9, c &#x2248; 20&#183;2 &#197;, &#946; &#x2248; 109&#183;5&#176;, Z = 4 dimers; R was 0&#183;046 and 0&#183;044 for No 5670 and 6039 respectively. The thiocyanate (4) has a similar cell, a 24&#183;12(1), b 12&#183;558(8), c 23&#183;244(4) &#197;, &#946; 110&#183;11(3)&#176;, Z = 4 dimers, R being 0&#183;044 for No 7956; one of the thiocyanate ligands (which bridge in Ag-SCN-Ag mode) is disordered. A second polymorph of the bromide (2b) (from a mixture of AgBr/saturated KBr in H2O) is also monoclinic, P 21/c, a 14&#183;121(8), b 25&#183;577(3), c 21&#183;968(2) &#197;, &#946; 125&#183;54(3)&#176;, Z = 4 dimers (R was 0&#183;047 for No 5715). Ag&#8211;As range between 2&#183;568(1) and 2&#183;633(1) &#197; throughout the series; in the isomorphous bromide and iodide, values increase slightly: 2&#183;578(1)&#8211;2&#183;611(1), cf. 2&#183;601(2)-2&#183;633(1) &#197; respectively. Ag&#8211;X are 2&#183;568(2)-2&#183;670(2) (Cl); 2&#183;688(2)&#8211;2&#183;715(2) (Br); 2&#183;828(2)&#8211;2&#183;856(1) &#197; (I); Ag-S, N for the ordered SCN group are 2&#183;646(3), 2&#183;255(6) &#197;. A redetermination of improved precision (R 0&#183;035, No 6030) is reported for the triphenylphosphine/thiocyanate analogue. The far-infrared spectra of &#91;(Ph3As)2Ag(&#181;-X)2Ag (AsPh3)2&#93; show v(AgX) bands at 185, 145 (X = Cl), 145, 130, 106 (X = Br) and 121 cm-1 (X = I). The splittings and band widths reflect a decrease in the degree of distortion of the Ag(&#181;-X)2Ag units from a symmetrically bridged structure from X = Cl to I. 
