Inert pair effect

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The term inert pair effect is often used in relation to the increasing stability of oxidation states that are 2 less than the group valency for the heavier elements of groups 13, 14, 15 and 16. The term "inert pair" was first proposed by Sidgwick in 1927.[1]
As an example in group 13 the +1 oxidation state of Tl is the most stable and TlIII compounds are comparatively rare. The stability increases in the following sequence:[2]

AlI < GaI < InI < TlI.

The situation in groups 14, 15 and 16 is that the stability trend is similar going down the group, but for the heaviest members, e.g. lead, bismuth and polonium both oxidation states are known.
The lower oxidation state in each of the elements in question has 2 valence electrons in s orbitals. On the face of it a simple explanation could be that the valence electrons in an s orbital are more tightly bound are of higher energy than electrons in p orbitals and therefore less likely to be involved in bonding. Unfortunately this explanation does not stand up. If the total ionization potentials(see below) of the 2 electrons in s orbitals (the 2d + 3d ionization potentials), are examined it can be seen that they increase in the sequence:

In < Al < Tl < Ga.
Ionization potentials for group 13 elements
kJ/mol
IP Boron Aluminium Gallium Indium Thallium
1st 800.6 577.5 578.8 558.3 589.4
2st 2427.1 1816.7 1979.3 1820.6 1971
3d 3659.7 2744.8 2963 2704 2878
(2d + 3d) 6086.8 4561.5 4942.3 4524.6 4849

The high IP(2d + 3d) of gallium is explained by d-block contraction, and the higher IP(2d + 3d) of thallium relative to indium, has been explained by relativistic effects.[3]

An alternative explanation of the inert pair effect by Drago in 1958[4] attributed the effect to low M-X bond enthalpies for the heavy p-block elements and the fact that it requires less energy to oxidize an element to a low oxidation state than to a higher oxidation state. This energy has to be supplied by ionic or covalent bonds, so if bonding to a particular element is weak, the high oxidation state may be inaccessible. Further work involving relativistic effects confirms this.[5]In view of this it has been suggested that the term inert pair effect should be viewed as a description rather than as an explanation.[2]

[edit] Steric activity of the lone pair

The chemical inertness of the s electrons in the lower oxidation state is not always married to steric inertness, (where steric inertness means that the presence of the s electron lone pair has little or no influence on the geometry of molecule or crystal). A simple example of steric activity is that of SnCl2 which is bent in accordance with VSEPR. Some examples where the lone pair appears to be inactive are Bismuth(III) iodide, BiI3, and the BiI63− anion. In both of these the central Bi atom is octahedrally coordinated with little or no distortion, in contravention to VSEPR theory.[6] The steric activity of the lone pair has long been assumed to be due to the orbital having some p character, i.e. the orbital is not spherically symmetric.[2] More recent theoretical work shows that this is not always necessarily the case. For example the litharge structure of PbO contrasts to the more symmetric and simpler rock salt structure of PbS and this has been explained in terms of PbII − anion interactions in PbO leading to an asymmetry in electron density. Similar interactions do not occur in PbS.[7] Another example are some thallium(I) salts where the asymmetry has been ascribed to s electrons on Tl interacting with antibonding orbitals.[8]

[edit] References

  1. ^ N.V. Sidgwick , The Electronic Theory of Valency" first published 1927
  2. ^ a b c Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements, 2nd Edition, Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4. 
  3. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  4. ^ Russell S. Drago (1958). "Thermodynamic Evaluation of the Inert Pair Effect". J Phys Chem 62 (3): 353 - 357. doi:10.1021/j150561a027. 
  5. ^ Schwerdtfeger P, Heath G A, Dolg M, Bennet M A (1992). "Low valencies and periodic trends in heavy element chemistry. A theoretical study of relativistic effects and electron correlation effects in Group 13 and Period 6 hydrides and halides". Journal of the American Chemical Society 114 (19): 7518-7527. doi:10.1021/ja00045a027. 
  6. ^ Ralph A. Wheeler and P. N. V. Pavan Kumar (1992). "Stereochemically active or inactive lone pair electrons in some six-coordinate, group 15 halides". Journal of the American Chemical Society 114 (12): 4776-4784. doi:10.1021/ja00038a049. 
  7. ^ Walsh A, Watson G W (2005). "The origin of the stereochemically active Pb(II) lone pair: DFT calculations on PbO and PbS". Journal of Solid State Chemistry 178 (5): 1422-1428. doi:10.1016/j.jssc.2005.01.030. 
  8. ^ Mudring A J, Rieger F (2005). "Lone Pair Effect in Thallium(I) Macrocyclic Compounds". Inorg. Chem. 44 (18): 6240 -6243. doi:10.1021/ic050547k. 

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