CALCULATED STRUCTURES AND RELATIVE STABILITIES OF FUROXAN, SOME 1,2-DINITROSOETHYLENES AND OTHER ISOMERS
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The structures and relative stabilities of furoxan and some of its isomers, e.g., the 1,2dinitrosoethylenes, have been determined by means of ab initio HarteeFock and MllerPlesset calculations. Geometries were optimized at the HF/321G, HF/631G* and MP2/631G* levels, and subsequently used for computing MP2/631G*, MP3/631G*, and MP4/631G* energies. The results are markedly affected by the inclusion of electronic correlation, which renders three of the isomers unstable. It also emphasizes the importance of a zwitterionic contribution to the structure of furoxan, which promotes ringopening through a cis 1,2dinitrosoethylene intermediate/transition state that has an MP4/631G*//MP2/631G* energy that is 31.6 kcal/mol above furoxan. Copyright 1992 John Wiley & Sons, Inc.