The charge transfer contribution is minimal in the ground state of these complexes. ( 27) The relationship is actually parabolic26 and becomes linear at only small energy differences.(28) For a discussion of bridging groups in inner-sphere electron transfer reactions see A.
The 1,2-cycloaddition of nitrosoarenes t o ketenimines producing 3-iminosubstituted-l,2oxazetidines has been found to proceed more rapidly if photosensitized conditions are employed. This data plus the specificity of the reaction allows for a reasonable postulation of the nonphotochemical room temperature reaction.The 1,2-cycloaddition reaction of diphenylketenc and p-substituted nitrosoarenes has been studied extensively by Staudinger and Jelogin (2) and by Kresze and Trede(3). These workers found that the reaction produces either 3-oxazetidinnnes (I) or 4-oxazetidinones (11) depending upon the substituent in the p-position of the nitrosoarene (Eq 1). If the nitrosoarene substituent is strongly electron donating @-methoxy and p-dimethylamino) the 4oxazetidinone is obtained while the 3oxazetidinone is obtained with all other substituents. Krwze and Trede (3) explained the production of the 4oxazetidinones as the result of a "polar addition" but ventured n o explanation for the formation of the 3oxazetidinones.
I I1
Eq. 1Recently, we reported (4) o n the reaction between nitrosoarenes and ketenimines (nitrogen analogs of ketenes). With these seemingly similar reagents only the 3iminosubstituted oxazetidinone (111) is obtained (Eq. 2).
Aus den Keteniminen (I) und den Nitroso‐Verbindungen (II) werden die Oxazetidine (III) erhalten, die in Benzophenon (IV) und die Carbodiimide (V) zerfallen.
Die Verbindung (Ia) wurde durch Reaktion von Chloro‐terpyridylplatin mit Ag‐nitrat in wässriger Lösung und Weiterreaktion des entstehenden Aquokomplexes mit 2‐Mercaptoäthanol als Nitrat erhalten.
Aus den Keteniminen (I) und den Nitrosobenzolen (II) bilden sich beim Stehen in Lösung die 3‐Imino‐1,2‐oxazetidine (III), die thermisch zu Benzophenon (IV) und Carbodiimiden (V) zerfallen.
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