Saturday, July 27, 2019

bond - What allows sulfur and phosphorus to expand their octet?


There are many compounds in which the stability of a molecule is not governed by the presence of octet configuration in central atom. In most of the cases the central atom is generally sulfur or phosphorus. In these cases either the central atom has 6 electrons, or sometimes the electron count exceeds 8 and 10 or 12 electrons in its valence electron shell.


This makes the concept of octet somewhat incorrect. My question is how can they increase their octet to such an extent?


Could someone explain this in relation with sulfur trioxide?



Answer



Whether sulfur or phosphorous actually expand their octet is contested within the chemistry community. Another term for this octet expansion is "hypervalency." You can find many works of research regarding hypervalency. The consensus, according to Wikipedia, is that both can expand their octets, but not to a significant extent. In other words, d-orbital utilization is low at best.


Regarding sulfur trioxide, this article may be of interest.



We find no evidence to support notions of p π –d π back-donation from oxygen to sulfur.




Regarding the octet concept, it's only a guideline at best, and nothing more. I wouldn't put too much stock into the concept. If you insist on using it, then only apply it to the following elements: $\ce{C, N, O}$, and $\ce{F}$. And note that for carbon, there are well known exceptions in organic chemistry - carbocations (which have less than an octet of electrons). Carbocations however tend to exist mainly as reactive intermediates. Therefore, a more nuanced statement might be $\ce{C, N, O}$, and $\ce{F}$, when involved in neutral and thermodynamically stable compounds, generally have 8 valence electrons.



this makes the concept of octet somewhat incorrect.



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