A Comparison of Structure and Stability between the Group 11 Halide Tetramers M4X4 (M = Cu, Ag, or Au; X = F, Cl, Br, or I) and the Group 11 Chloride and Bromide Phosphanes (XMPH3)4

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Abstract
The tetramers of the group 11 (I) halides, M4X4 (M = Cu, Ag, or Au; X = F, Cl, Br, or I), and corresponding group 11 (I) phosphanes, chloride and bromide (XMPH3)4 (X = Cl or Br), are investigated by the density functional theory. All coinage metal(I) halide tetramers adopt squarelike ring structures with an out-of-plane distorted (butterfly) D2d symmetry. These structures are much lower in energy than the more compact cubelike Td arrangements, which maximize dipole−dipole interactions and more closely resemble the solid-state structures of the copper and silver halides. Phosphine coordination completely changes the structures of these M4X4 clusters. The copper(I) and silver(I) phosphane chloride and bromide tetramers adopt a heterocubane structure, slightly preferred over a step (ladder-type)-cluster structure well-known in the coordination chemistry of such compounds. In stark contrast, gold(I) phosphane chloride and bromide tetramers prefer assemblies of linear XAuPH3 units with direct gold−gold contacts, resulting in a square planar, centered trigonal planar, or tetrahedral gold core.

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