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There are oxidation states from -4 to +8

Why do the negative oxidation states not go all the way down to -8? I mean if an atom is hypervalent meaning that it can have more than an octet than that means it can have potentially 8 bonds(counting a double bond as 2 bonds and a triple bond as 3 bonds respectively) to other atoms more electronegative than itself and thus Xenon can have a +8 oxidation state and some metals can as well.

Doesn't that also mean that a hypervalent atom can have 8 bonds to other atoms less electronegative than itself and thus have a -8 oxidation state?

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  • $\begingroup$ Actually it's now -5 to +9. $\endgroup$
    – Oscar Lanzi
    Jul 22 at 16:42

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Why do the negative oxidation states not go all the way down to -8?

Let's think about what we would need for this to occur - i.e. an oxidation state of -8.

We would need a central atom that has considerable electronegativity - one that is at least more electronegative than its attached atoms. This already excludes numerous molecules; most molecules' central atoms are, on a relative basis, more electropositive rather than electronegative.

In addition, this atom would need to have one of the following configurations; "allocated" refers to the assignment of oxidation state - since oxidation states are assigned on the premise that all bonding is ionic - the more electronegative element in a bonding configuration is "allocated" all the bonding electrons in the calculation of oxidation states. I.e. in H2O, the oxygen would be allocated both pairs of bonding electrons in the H-O bonds, and oxygen would then "have" 8 electrons, and its oxidation state would be -2.

1 valence electron and be "allocated" 9 electrons

2 valence electrons and be "allocated" 10 electrons

3 valence electrons and be "allocated" 11 electrons,

and on the other extreme:

6 valence electrons and be "allocated" 14 electrons,

7 valence electrons and be "allocated" 15 electrons,

8 valence electrons and be "allocated" 16 electrons.

As we can see, the first set of criteria are basically incompatible. Elements only having 1 or 2 valence electrons are going to be small (on a relative basis). These elements would also much rather be oxidized than reduced. Oxidation allows these elements to easily become isoelectronic with a noble gas.

The other set of criteria for a negative 8 oxidation state is also hard to fulfill. None of the group 6 elements except the possibility of sulfur and elements below it are hypervalent - i.e. they can accommodate more than 8 valence electrons. Even if we consider sulfur as able to accommodate 12 valence electrons (as some depictions of sulfuric acid suggest) we must remember that sulfur is not very electronegative and unlikely to be allocated any electrons.

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  • $\begingroup$ Sulfur is more electronegative than quite a few elements, especially metals, but also the oxygen group elements below sulfur, Nitrogen group elements below N, Carbon group elements, Boron group elements, Xenon, Iodine, and Astatine. $\endgroup$
    – Caters
    Aug 16, 2014 at 23:23
  • $\begingroup$ Right, but I can't think of any molecules or ions in which sulfur is the central element and metals are ligands, the other way around yes. Such as silver sulfide. $\endgroup$
    – Dissenter
    Aug 16, 2014 at 23:24
  • $\begingroup$ Doesn't the possibility of a -8 oxidation state only require that a hypervalent atom has 8 bonds(covalent(with a double bond counted as 2 and a triple bond counted as 3 respectively) or ionic) to 8 atoms less electronegative than itself, not that it is the central atom? $\endgroup$
    – Caters
    Aug 18, 2014 at 23:58
  • $\begingroup$ Well, you also have to consider how many electrons the element has in its valence. $\endgroup$
    – Dissenter
    Aug 19, 2014 at 3:25
  • $\begingroup$ right but it has to have 8 bonds to something less electronegative than itself(with a double bond counted as 2 and a triple bond as 3 respectively) whether they are covalent, ionic, or both(even though it is rare to have both types of bonds in the same compound unless you are talking about a hydroxide or something along those lines.) $\endgroup$
    – Caters
    Aug 19, 2014 at 14:14

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