
TY  - JOUR
A1  - Bott, Raymond C. 
A1  - Bowmaker, Graham A. 
A1  - Buckley, Robbie W. 
A1  - Healy, Peter C. 
A1  - Perera, M. C. Senake 
T1  - Synthesis, Structures and Spectroscopic Properties of 1 : 1 Complexes of Gold(I) Halides with Trimesitylphosphine
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 2000
VL  - 53
IS  - 3
SP  - 175
EP  - 181
KW  - X-Ray crystallography; gold complexes; phosphine ligands; synthesis.
UR  - https://doi.org/10.1071/CH99165 
N2  - Monomeric two-coordinate gold(I) complexes, &#91;Au(P(mes)3)X&#93; (P(mes)3 = tris(2,4,6-trimethylphenyl)phosphine, X = Cl, Br and I), have been prepared and characterized by single-crystal X-ray structure determinations, far-infrared spectroscopy and solution and solid-state CPMAS 31 P n.m.r. spectroscopy. X-Ray structure determinations show that crystals obtained from solutions of &#91;NBu4&#93; &#91;AuX2&#93; and P(mes)3 in acetonitrile for X = Cl, Br and I and in dimethylformamide (dmf) for X = Br and I form an isomorphous series of complexes, crystallizing in space group P21/c with a &ordf; 8, b &ordf; 22, c &ordf; 13 &#197;, b &ordf; 98&#x02DA; (a form). Crystallization of the chloride from dimethylformamide yields the solvated complex &#91;Au(P(mes)3)X&#93;&#183;(dmf) in space group P2/a with a 15.224(2), b 10.070(1), c 18.210(4) &#197;, b 100.42(2)&#x02DA;. Electrochemical synthesis of the complexes for X = Cl and Br yield two new crystalline phases; the chloride in space group P21/c with a 10.249(2), b 8.189(2), c 31.844(3) &#197;, b 91.68(1)&#x02DA; (b form) and the bromide in space group Pbca with a 19.208(4), b 15.586(3), c 16.962(4) &#197; ( g form). The Au&#8211;P bond lengths increase in the order Cl &#60; Br &#60; I with distances c. 0.02&#8211;0.03 &#197; longer than average values for other &#91;Au(PR3)X&#93; complexes, reflecting steric congestion by the P(mes)3 ligand. For the unsolvated complexes, the Au&#8211;X distances are c. 0.02 &#197; shorter than average values. For the Cl/dmf solvate, both Au&#8211;P and Au&#8211;X bond lengths increase. For the a complexes, far-infrared spectra show n(Au 35,37 Cl) 336, 329 cm &#8211;1 , n(AuBr) 234 cm &#8211;1 and n(AuI) 195 cm &#8211;1 and solid-state 31 P CPMAS n.m.r. spectra yield broad peaks with d&#8211;3.9 (Cl), &#8211;0.6 (Br) and +6.0 I). For the Cl/dmf solvate, n(Au 35,37 Cl) are 334, 327 cm &#8211;1 and d is &#8211;4.4. Solution 31 P n.m.r. spectra in CDCl3 give sharp single peaks at d &#8211;5.0 (Cl), &#8211;1.4 (Br) and +5.5 (I) with the similarity of the values with those for the solid-state spectra consistent with similar conformational structures for the &#91;Au(P(mes)3)X&#93; molecules in the two states. 
ER  -

