Apicophilicity is the phenomenon in which

electronegative Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...

substituents of

trigonal bipyramidal In chemistry, a trigonal bipyramid formation is a molecular geometry with one atom at the center and 5 more atoms at the corners of a triangular bipyramid. This is one geometry for which the bond angles surrounding the central atom are not ident ...

pentacoordinate compounds prefer to occupy apical (axial) positions (L_ap).IUPAC Gold Book
/ref> The term "apicophilicity" was first proposed by Earl L. Muetterties in 1963 for the structural analysis of pentacoordinate

phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...

fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an inorganic, monatomic anion of fluorine, with the chemical formula (also written ), whose salts are typically white or colorless. Fluoride salts ...

s by ¹⁹F NMR. Since the apical bonding of a pentacoordinate typical ( group 1, 2, 13-18) element compound consists of a 3-center-4-electron bond, in which the

electron density In quantum chemistry, electron density or electronic density is the measure of the probability of an electron being present at an infinitesimal element of space surrounding any given point. It is a scalar quantity depending upon three spatial ...

is localized on two apical

substituent A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and '' functional group'', as well as '' ...

s, an arrangement in which electronegative substituents occupy apical positions is more stable. The apicophilicity of a substituent is defined as the difference in energy between two

isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. ...

ic structures in which the substituent occupies an apical position and an equatorial position (L_eq). Experimentally, instead of direct measurement of the energy difference, which is usually difficult to measure, the relative energy barriers for

pseudorotation In chemistry, a pseudorotation is a set of intramolecular movements of attached groups (i.e., ligands) on a highly symmetric molecule, leading to a molecule indistinguishable from the initial one. The International Union of Pure and Applied Che ...

of isomers are used for determination of the apicophilicity scale. Some experimental and theoretical studies have been made to measure relative apicophilicities for various substituents. The apicophilicity of a substituent mainly depends on its electronegativity, but some other factors can also have an effect. A bulky substituent prefers equatorial positions, which are more distant from other substituents. A substituent with π-bonding ability also prefers equatorial positions. The use of multidentate ligands can also control the arrangement of substituents. For example, a bidentate ligand with a five-membered ring structure greatly stabilizes the arrangement in which their two coordination sites occupy equatorial and an apical position. Image:Phosphorus-chloride-tetrafluoride-3D-balls.png, PClF₄ Image:Phosphorus-dichloride-trifluoride-3D-balls.png, PCl₂F₃ Image:Phosphorus-trichloride-difluoride-3D-balls.png, PCl₃F₂ Image:Phosphorus-tetrachloride-fluoride-3D-balls.png, PCl₄F

References

Chemical properties