The structures of the series of two-coordinate gold(I) complexes {(Me(2)PhP)AuX}(n) where X is Cl, Br, or I have been examined by X-ray diffraction. The chloro complex crystallized in two separate polymorphic forms. Colorless hexagonal blocks of {(Me(2)PhP)AuCl}(3) crystallized in the monoclinic space group P2(1)/m with a = 12.141(4) Å, b = 8.433(2) Å, c = 14.834(3) Å, and beta = 94.15(2) degrees at 130 K with Z = 2. Refinement of 2837 reflections and 177 parameters yielded R = 0.066 and R(w) = 0.069. The complex consists of three nearly linear P-Au-Cl units that are connected by Au-Au contacts at 3.091(2) and 3.120(2) Å. Colorless prisms of {(Me(2)PhP)AuCl}(2) form in the orthorhombic space group P2(1)2(1)2(1) as described earlier (Cookson, P. D.; Tiekink, E. R. T. Acta Crystallogr. 1993, C49, 1602). The two nearly linear P-Au-Cl units are staggered and connected through a Au-Au bond (3.230(2) Å). Colorless rectangular prisms of {(Me(2)PhP)AuBr}(2) form in the monoclinic space group P2(1) with a = 9.572(5) Å, b = 8.757(3), and c = 12.915(7) at 130 K with Z = 2. Refinement of 2469 reflections with 118 parameters yielded R = 0.080 and R(w) = 0.084. {(Me(2)PhP)AuI}(2) is isomorphous with the bromo complex with a = 9.736(2) Å, b = 8.890(2) Å, and c = 13.160(5) Å at 130 K with Z = 2. Refinement of 2796 reflections with 119 parameters yielded R = 0.052 and R(w) = 0.058. These complexes are similar to the chloro dimer but with altered orientations of the phenyl substituent. The predicted order of ligand effects (Cl > Br > I) on Au-Au distances from quasi-relativistic calculations is borne out in the experimental values: 3.230 Å (Cl); 3.119 Å (Br); 3.104 Å (I). In dichloromethane, these complexes dissociate into monomeric units but there is some evidence for the presence of dimers in concentrated solutions of the iodide compound.
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Toronto et al. (1996) studied this question.