Katzin, Leonard

Leonard Katzin I want to make two comments, one on this last point in relation to the point that Dr. Margerum made about substituents. Chromium (I II) in the hexahyd rated state is quite resistant to penetration of the coordination shell by nitrate ion. Yet if one takes the% violet chromium nitrate hexahydrate in solid state and treats it with liquid tributylphosphate, within a matter of minutes one gets chromium compound in solution by the mechanism of substituting tributylphosphate for water. So this reaction is fast. This initial solution is violet Within the space of an hour or two it is green. And we have had for some years now infrared evidence that this color change is accompanied by penetration of the nitrate ion into the coordination sphere (4). So this again is a matter of the substituent s changing the relationship of the water. 

Leonard Katzin My first point refers to the question of the nitrate absorption spectrum. If one goes back a decade or more in the literature, there are observations on this peak of a nitrate in nonaqueous solutions of inorganic salts, and I don t believe that the wave length stays fixed. It shifts toward shorter wave lengths—not a great deal, but perceptibly (5). 

Leonard 1. Katzin, Argonne National Laboratory, Argonne, Illinois... 

Chemistry Division, Argoime National Laboratory, USA Leonard I. Katzin... 

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