Wednesday, May 9, 2018

bond - What is charge shift bonding?



Can someone explain to me charge shift bonding? I recognize that it is proposed as another domain of bonding - one different from ionic and covalent bonding. I am also told that $\ce{C-F}$ exhibits charge shift bonding. But why—and firstly, what exactly is charge shift bonding? All the literature I have consulted are at too high of a level for me, for example this 1992 article in the Journal of the American Chemical Society.



Answer



OK, this was a new one to me too, but I found a few resources which might be useful:



The basic idea is this. Most bonds are ionic (i.e., both atoms are charged, but electrostatically attracted) or covalent (i.e., the electron pair is shared).


(This is largely cribbed from the Comp. Org. Chem. blog post. Thanks to Steven Bachrach)


If we were writing a multi-configurational wavefunction to describe the bond, we might have something like:


$$\psi(\mathrm{VB}) = c_1\psi_\mathrm{covalent} + c_2\psi_{\ce{A+B-}} + c_3\psi_{\ce{A-B+}}$$


So normally, we'd look at which is the dominant configuration - maybe it's the covalent one ($c_1$) or one of the ionic ones ($c_2$ or $c_3$). Instead, sometimes the covalent form isn't even stabilizing!


From my perspective, the classic example given for this charge-shift bond is $\ce{F2}$ which of course has many $\pi^*$ anti-bonding electrons, so the classical bond order is 1, but ignores that there's a lot of antibonding character. But you can't really consider $\ce{F2}$ an ionic compound!



I think the big question is the future - can this new type of bonding show general predictability and utility. Clearly most chemists have a general intuition (if sometimes wrong) of covalent and ionic bonding. Besides the authors, I'm not sure if anyone else has an intuition of charge-shift systems.


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