Explain the stereochemistry of the following:
(1) [Au(CN)2]+. (2)[HgI3]-
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The stereochemistry of the following compounds is discussed.
Explanation:
1)
- Au+ almost always forms linear complexes but many of these formally two coordinate complexes. The ability of Au+ to form linear complexes with cyanide is even used to selectively extract metallic gold from low grade ores. The stability of [Au(CN)2]- means that the dissolution of metallic gold in aqueous cyanide is hermo dynamically favorable under aerobic conditions.
4 Au + 8 CN− + O2 + 2 H2O ⟶ 4 [Au(CN)2]− + 4 OH
- Although it is rare for most metals, this coordination number is surprisingly common for d10 metal ions, especially Cu+, Ag+, Au+, and Hg2+.
- An example is the [Au(CN)2]− ion, which is used to extract gold from its ores.
- As expected based on VSEPR considerations, these complexes have the linear L–M–L structure shown here.
2.
- Hg2+, like Au+, benefits from relativistic effects and more commonly forms two-coordinate complexes with a linear geometry.
- Among these is [Hg(CN)2]. However, its preference for linearity is not as rigid as for Au+ and so complexes with a variety of coordination geometries are known.
- Although it is also rare, this coordination number is encountered with d10 metal ions such as Cu+ and Hg2+. Among the few known examples is the HgI3− ion. Three-coordinate complexes almost always have the trigonal planar structure expected from the VSEPR model.
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