Square planar molecular geometry
The square planar molecular geometry in chemistry describes the stereochemistry (spatial arrangement of atoms) that is adopted by certain chemical compounds. As the name suggests, molecules of this geometry have their atoms positioned at the corners of a square on the same plane about a central atom.
The addition of two ligands to linear compounds, ML2, can afford square planar complexes. For example, XeF2 adds fluorine to give square planar XeF4.
In principle, square planar geometry can be achieved by flattening a tetrahedron. As such, the interconversion of tetrahedral and square planar geometries provides an intramolecular pathway for the isomerization of tetrahedral compounds. This pathway does not operate readily for hydrocarbons, but tetrahedral nickel(II) complexes, e.g. NiBr2(PPh3)2, undergo this change reversibly.
Square planar geometry can also be achieved by the removal of a pair of ligands from the z-axis of an octahedron, leaving four ligands in the xy plane. For transition metal compounds, the crystal field splitting diagram for square planar geometry can thus be derived from the octahedral diagram. The removal of the two ligands stabilizes the dz2 level, leaving the dx2−y2 level as the most destabilized. Consequently, the dx2−y2 remains unoccupied in complexes of metals with the d8 configuration. These compounds typically have 16 valence electrons (eight from ligands, eight from the metal).
Numerous compounds adopt this geometry, examples being especially numerous for transition metal complexes. The noble gas compound XeF4 adopts this structure as predicted by VSEPR theory. The geometry is prevalent for transition metal complexes with d8 configuration, which includes Rh(I), Ir(I), Pd(II), Pt(II), and Au(III). Notable examples include the anticancer drugs cisplatin [PtCl2(NH3)2] and carboplatin. Many homogeneous catalysts are square planar in their resting state, such as Wilkinson's catalyst and Crabtree's catalyst. Other examples include Vaska's complex and Zeise's salt. Certain ligands (such as porphyrins) stabilize this geometry.
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