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MARGINALIA

Hi O Silver

Roald Hoffmann

Charge It, Please

Chemists are always changing things. How to tune the propensity of a given oxidation state to oxidize or reduce? One way to do it is by changing the charge on the molecule that contains the oxidizing or reducing center. The syntheses of the silver fluorides cited above contain some splendid examples of this strategy. Let me use Bartlett's words again, just explaining that "electronegativity" gauges in some rough way the tendency of an atom to hold on to electrons. (High electronegativity means the electron is strongly held, low electronegativity that it is weakly held.)

Bartlett writes:

It's easy to make a high oxidation state in an anion because an anion is electron-rich. The electronegativity is lower for a given oxidation state in an anion than it is in a neutral molecule. That in turn, is lower than it is in a cation. If I take silver and I expose it to fluorine in the presence of fluoride ion, in HF, and expose it to light to break of F2 to atoms, I convert the silver to silver(III), AgF4-. This is easy because the AG(III) is in an anion. I can then pass in boron trifluoride and precipitate silver trifluoride, which is now a much more potent oxidizer than AgF4- because the electronegativity in the neutral AgF3 is much higher than it is in the anion. If I can now take away a fluoride ion, and make a cation, I drive the electronegativity even further up. With such a cation, for example, AgF2+, I can steal the electron from PtF6- and make PtF6.... This is an oxidation that even Kr(II) is unable to bring about.

Simple, but powerful reasoning. And it works.





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