The Oxidation States of Tin and Relative Stabilities of Tin and Lead

By Daniel Rodman
All Rights Reserved

Abstract

Figure 1. Tin(IV) iodide and Tin(II) iodide, respectively.

The tin iodide compounds with oxidation states of +4 and +2 are both easily prepared in the lab, and have similar stabilities, although vastly different in structure and electronic configuration. The tin(II) iodide complex is sp3 hybridized with tetrahedral geometry, common to the lighter elements in group 14. Tin(IV) iodide is an example of an ns2np2 electronic configuration in which there is an inert pair of electrons in the s2 orbital that is not subjected to promotion to a higher energy orbital. Ammonium hexachloroplumbate(IV) and hexachlorostannate(IV) are both examples of an ns2np2 electronic configuration that have promoted their electrons to higher energy levels for bonding and exhibit a coordination of six. However, the tin complex is much more stable, and less likely to be reduced compared to its lead counterpart. INTRODUCTION The transition metals are generally regarded for their multiple oxidation states, typically +2 or +3. However, it is not uncommon to find elements of the main group exhibiting a range of oxidation states as well. Group 14 elements are considered by some to be the most important of all, providing the building blocks of life as well as a structure for our physical world. All elements in group 14 form binary compounds with other elements, such as carbon dioxide. The electron configuration of this group is ns2np2, and as it suggests, the dominant oxidation state is +4. The lightest p-block elements are non-metals. An increase in metallic properties is observed when looking down the groups due to a decrease in ionization energy and an increase in ionic radius.1 RESULTS AND DISCUSSION

Figure 2. Ammonium Hexachlorostannate(IV).

The electronic configuration ns2np2 found in group 14 elements, in which two paired electrons reside in the s-orbital, while two unpaired electrons reside in the px and py orbitals. In the lighter elements, carbon, silicon, and germanium, one electron from the s-orbital is easily promoted to the pz orbital. This creates four orbitals with one unpaired electron in each, allowing the elements to make four covalent bonds that are hybridized sp3. These sp3 bonds are rather strong and have high enthalpies, which is why they exhibit the stability seen in compounds they form. Tin(IV) iodide is a molecule with tetrahedral geometry, and an example of a heavier group 14 element with sp3 hybridized bonds. The ammonium hexachlorostannate(IV) and ammonium hexachloroplumbate(IV) complexes prepared are examples of a six coordinate group 14 complexes, in which the bonds are ionic in character, and utilize d-orbitals not present in the lighter elements.2 Ammonium hexachloroplumbate(IV) is much more difficult to form compared to the tin complex, prepared by a redox reaction of lead(II) chloride in the presence of elemental chlorine. As the elements get larger down the group, they become increasingly more metallic as the valence band gap becomes smaller. This is why silicon and germanium are used as semi-conductors, while carbon is considered an insulating material.1 The ns2np2 electronic configuration in which two paired electrons reside in the s-orbital and two unpaired electrons reside in two of the three p-orbitals can make two covalent bonds, which is seen in tin(II) and lead(II) compounds. The two paired electrons in the s-orbital are referred to as an inert pair, and their effect is seen in Sn and Pb compounds when the +2 oxidation state becomes much more stable. Lead is generally found in the +2 oxidation state, as +4 lead compounds are easily reduced.

Figure 3. Ammonium Hexachloroplumbate(IV).

EXPERIMENTAL Tin(IV) iodide. Tin (119 mg, 1.00 mmol) and iodine (475 mg, 1.87 mmol) were combined in a reaction tube with methylene chloride (6.0 mL). The reaction mixture was heated to a mild reflux with a hot water bath for ~40 min until the disappearance of the violet color of iodine. The warm solution was gravity filtered and the reaction tube was washed with methylene chloride (200 L) and the filtrate was collected. A boiling stone was added to the filtrate and the soln was concentrated to ~2 mL. The resulting solution was cooled in an ice-water bath and the orange-red crystals were collected by vacuum filtration. The product, tin(IV) iodide, was allowed to dry and weighed (0.1650 g, 0.2634 mmol, 26.3% yield). Tin(II) iodide. Tin (80 mg, 0.68 mmol) was placed into a 10 mL beaker. To the beaker, conc HCl (1.0 mL) and a soln of CuSO4 (2-3 drops, 0.1M) was added. The beaker was put on a hot plate and covered with a watch glass. The mixture was heated, with stirring, to just below boiling. While the reaction between the tin and HCl was underway, granular zinc (100 mg, 1.53 mmol) was added to a separate 10 mL beaker with DI water (1 mL). Iodine crystals (100 mg,

0.40 mmol) were added to the beaker, which was cooled in an ice-water bath. The mixture was stirred while a brown color started to develop, and continued until the soln turned into a light yellow color, indicating the completion of the rxn. The ZnI2 soln was gravity filtered into another 10 mL beaker. The HCl mixture was then filtered and added dropwise directly to the ZnI2 soln, instantly forming an orange-yellow precipitate of SnI2. The soln was cooled in an ice-water bath and the precipitate collected by vacuum filtration. The final product, tin(II) iodide, was allowed to dry and weighed (0.0914 g, 0.2454 mmol, 36.1% yield). Ammonium hexachlorostannate(IV). Anhydrous SnCl4 (0.2 mL, 0.0898 mol) was added to a tared 10 mL beaker. Water (70 L) was added dropwise to the beaker. A soln of NH4Cl (35 mg, 0.65 mmol) dissolved in water (100 L) was added to the mixture, immediately resulting in the product, (NH4)2SnCl6. The crystals were collected by vacuum filtration and washed with two portions of cold ethanol (0.5 mL) and two portions of ether (0.5 mL). The product was allowed to dry. Ammonium hexachloroplumbate(IV). In a 10 mL Erlenmeyer flask, a suspension of PbCl2 (100 mg, 0.36 mmol) in HCl (1.5 mL, 12M) was prepared. The flask was cooled in an icewater bath. The PbCl2 was gassed with elemental chlorine while connected to a NaOH trap. When the PbCl2 was fully dissolved the liquor was cooled in an ice-water bath, and NH4Cl (40 mg, 0.75 mmol) was added, and left to stand for ~10 min. The product, ammonium hexachloroplumbate(IV), was collected by vacuum filtration, washed with two portions of cold ethanol (0.5 mL) and two portions of ether (0.5 mL). It was allowed to dry and weighed (0.8084 g) CONCLUSION The tin iodide compounds with oxidation states of +4 and +2 are both easily prepared in the lab, and have similar stabilities, although vastly different in structure and electronic configuration. The tin(II) iodide complex is sp3 hybridized with tetrahedral geometry, common to the lighter elements in group 14. Tin(IV) iodide is an example of an ns2np2 electronic configuration in which there is an inert pair of electrons in the s2 orbital that is not subjected to promotion to a higher energy orbital. Ammonium hexachloroplumbate(IV) and hexachlorostannate(IV) are both examples of an ns2np2 electronic configuration that have promoted their electrons to higher energy levels for bonding and exhibit a coordination of six. However, the tin complex is much more stable, and less likely to be reduced compared to its lead counterpart. REFERENCES 1) Atkins, P. Inorganic Chemistry, 4th Edition: W.H. Freeman and Co.: New York, 2006, pp. 317-329 2) Nakamura, D. The Nature of the Metal-Ligand Bonds in Hexahalostannates(IV) and Ammonium Hexachloroplumbate(IV) Studied by the Pure Quadrupole Resonance of Halogens, Bull. Chem. Soc. Jpn., 1963. 36(12)