Reply to More on CIO and Related Radicals

Jun 6, 2008 - Similar to its electron-dot progenitor, the electron-quartet representation invokes the inert gas magic and ... Brooklyn College of CUNY...
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Letters The authors reply: We thank Prof. Jensen for bringing Dr. Linnett’s work on oxygen–halogen diatomics to our attention. We were not aware that quartet theory had been applied in this way. Our article was intended to resolve the ambiguity in formal charge and electronegativity arguments in Lewis electron dot structures, but can equally be applied to the interpretation of the quartet structures. We note, for example, that Linnett indicates a single-bonded O–F structure should be favored based on his analysis of bond stretching frequencies (ref 5 in Jensen’s response). This was a clever use of indirect evidence to circumvent the technological limitations present at the time it was made, but it contradicts the electronic structure calculations we report. Jensen notes Pimentel and Spratley’s observation that quartet theory was introduced perhaps 20 years too late. The full quote (ref 6 in Jensen’s response) is perhaps apropos, “...it is possible that the electron-quartet scheme was born twenty

years too late to fall into everyday use. Similar to its electron-dot progenitor, the electron-quartet representation invokes the inert gas magic and ignores again the energy differences between the s and p orbitals.” These are in fact the failings of Lewis electron dot theory that our article sought to address and can equally address for quartet theory. Supporting JCE Online Material

http://www.jce.divched.org/Journal/Issues/2008/Jun/abs783_2.html Full text (HTML and PDF) Mark Kobrak and Warren Hirsch Department of Chemistry Brooklyn College of CUNY Brooklyn, NY 11210-2889 [email protected]; [email protected]

© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 6  June 2008  •  Journal of Chemical Education

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