
TY  - JOUR
A1  - Hart, Robert D. 
A1  - Bowmaker, Graham A. 
A1  - Silva, Eban N. de 
A1  - Skelton, Brian W. 
A1  - White, Allan H. 
T1  - Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXV Synthesis, Spectroscopy and Structural Systematics of Some 1 : 3 Adducts of Copper(I) Compounds with Triphenylarsine, [(Ph<emph tye="8">3</emph>As)<emph tye="8">3</emph>CuX], X = Cl, Br, I, ONO<emph tye="8">2</emph>
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1997
VL  - 50
IS  - 6
SP  - 553
EP  - 566
KW  - 
UR  - https://doi.org/10.1071/C96032 
N2  - Crystallization of some copper(I) salts, CuX, with triphenylarsine in 1 : 3 stoichiometry from acetonitrile has yielded an array of adducts, &#91;(Ph3As)3CuX&#93;, characterized by room-temperature single crystal X-ray structure determinations. &#91;(Ph3As)3CuCl&#93; (1) has been characterized in two unsolvated phases, &#945; and &#946;, the second form previously recorded as monoclinic, P21/n, Z = 8. The &#8216;&#945;&#8217; phase, like the bromide (2) and iodide (3), adopts the trigonal P3 array, widespread among many &#91;(Ph3E)3MX&#93; adducts with a &#x2248; 19, c &#x2248; 11 &#197;; conventional R on F was 0&#183;037, 0&#183;041, 0&#183;056 for No 3458, 3259, 3434 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) reflections for these three adducts respectively. A further form, &#947;, is a toluene hemisolvate, monoclinic, P21/c, a 21&#183;490(5), b 10&#183;218(7), c 24&#183;901(6) &#197;, &#946; 117&#183;53(2)&#176;, Z = 4, R 0&#183;057 for No 7207. The nitrate (4), obtained as a monosolvate from methanol, is monoclinic, P21/n, a 15 &#183;115(9), b 23&#183;201(9), c 14&#183;170(14) &#197;, &#946; 92&#183;56(7)&#176;, Z = 4, R 0&#183;049 for No 5476. In all compounds, the copper atom is four-coordinate, E3CuX, the nitrate in (4) being -ONO2 unidentate. The CuX bond lengthsr(CuX) in &#91;(Ph3E)3CuX&#93; (X = Cl, Br, I) show a decrease from the Ph3P to the corre3sponding Ph3As compound, and this is consistent with the observed increase in the v(CuX) wavenumbers in the far-infrared spectra. These trends are both consistent with an increase in the CuX bond strength from the Ph3P to the Ph3As complexes, and possible reasons for this are discussed. 
ER  -

