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Issue 18, 1994
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Preparation of N(SeCl)2+X(X = SbCl6 or FeCl4), F3CCSeNSeCCF3+SbCl6, F3CCSeNSeCCF3, F3CCSeNSeCCF3 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3. Electron diffraction study of F3CCSeSeCCF3 and crystal structure of the eight-membered heterocycle F3CCSeSeC(CF3)C(CF3)SeSeCCF3

Abstract

The salts N(SeCl)2+SbCl61 and N(SeCl)2+FeCl42 were synthesized by reaction of SeCl3+ X(X = SbCl6 or FeCl) with N(SiMe3)3; 1 was also formed by reaction of Se2NCl3 with SbCl5. Reaction of 1 with SnCl2 and F3CCCCF3 led to the formation of F3C[graphic omitted]CF3+ SbCl63. In this reaction the Se2N + cation is a likely intermediate because SnCl2 seems to be essential for chloride abstraction in the first reaction step to generate Se2N+in situ which then adds F3CCCCF3 to yield 3. Compound 3 is a useful building block to generate selenium compounds such as F3C[graphic omitted]CF34, F3C[graphic omitted]CF35 and F3C[graphic omitted]CF36. The heterocycle 5 was shown by electron diffraction to have an approximately planar four-membered ring structure. The structure of compound 6 was determined by X-ray crystallography: orthorhombic, space group Pbca, a= 10.1920(21), b= 13.0615(20) and c= 22.050(5)Å. In order to rationalize the structures of 5 and the cation F3C[graphic omitted]CF3+, ab initio calculations were made on model compounds in which the CF3 groups were replaced by a fluorine atom (i.e.F[graphic omitted]F for 5and F[graphic omitted]F+ for the cation in 3). In addition, mass spectrometric experiments were performed in order to examine the structures and stabilities of the unligated cation F3C[graphic omitted]CF3+ as well as its neutral counterpart. The existence of the neutral radical 4 was established by means of neutralization–reionization mass spectrometry.

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J. Chem. Soc., Dalton Trans., 1994, 2705-2712
Article type
Paper

Preparation of N(SeCl)2+X(X = SbCl6 or FeCl4), F3CCSeNSeCCF3+SbCl6, F3CCSeNSeCCF3, F3CCSeNSeCCF3 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3. Electron diffraction study of F3CCSeSeCCF3 and crystal structure of the eight-membered heterocycle F3CCSeSeC(CF3)C(CF3)SeSeCCF3

K. B. Borisenko, M. Broschag, I. Hargittai, T. M. Klapötke, D. Schröder, A. Schulz, H. Schwarz, I. C. Tornieporth-Oetting and P. S. White, J. Chem. Soc., Dalton Trans., 1994, 2705
DOI: 10.1039/DT9940002705

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