Preparation of N(SeCl)2 +X- (X = SbCl6 or FeCl4), F3CCSeNSeCCF3 +SbCl6 -, F3CCSeNSeCCF3, F3CCSeNSeCCF3 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3. Electron diffraction study...

Konstantin B. Borisenko, Matthias Broschag, I. Hargittai, Thomas M. Klapötke, Detlef Schröder, Axel Schulz, Helmut Schwarz, Inis C. Tornieporth-Oetting, Peter S. White

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Abstract

Full title: 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. The salts N(SeCl)2 +SbCl6 - 1 and N(SeCl)2 +FeCl4 - 2 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 F3CCSeNSeCCF3 + SbCl6 - 3. 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 F3CCSeNSeCCF3 4, F3CCSeSeCCF3 5 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3 6. 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 F3CCSeNSeCCF3 +, ab initio calculations were made on model compounds in which the CF3 groups were replaced by a fluorine atom (i.e. FCSeSeCF for 5and FCSeNSeCF+ for the cation in 3). In addition, mass spectrometric experiments were performed in order to examine the structures and stabilities of the unligated cation F3CCSeNSeCCF3 + as well as its neutral counterpart. The existence of the neutral radical 4 was established by means of neutralization-reionization mass spectrometry.

Original languageEnglish
Pages (from-to)2705-2712
Number of pages8
JournalJournal of the Chemical Society, Dalton Transactions
Issue number18
DOIs
Publication statusPublished - 1994

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Electron diffraction
Cations
Selenium Compounds
Fluorine
X ray crystallography
Mass spectrometry
Chlorides
Salts
Crystal structure
Atoms
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

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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... / Borisenko, Konstantin B.; Broschag, Matthias; Hargittai, I.; Klapötke, Thomas M.; Schröder, Detlef; Schulz, Axel; Schwarz, Helmut; Tornieporth-Oetting, Inis C.; White, Peter S.

In: Journal of the Chemical Society, Dalton Transactions, No. 18, 1994, p. 2705-2712.

Research output: Contribution to journalArticle

Borisenko, Konstantin B. ; Broschag, Matthias ; Hargittai, I. ; Klapötke, Thomas M. ; Schröder, Detlef ; Schulz, Axel ; Schwarz, Helmut ; Tornieporth-Oetting, Inis C. ; White, Peter S. / Preparation of N(SeCl)2 +X- (X = SbCl6 or FeCl4), F3CCSeNSeCCF3 +SbCl6 -, F3CCSeNSeCCF3, F3CCSeNSeCCF3 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3. Electron diffraction study... In: Journal of the Chemical Society, Dalton Transactions. 1994 ; No. 18. pp. 2705-2712.
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title = "Preparation of N(SeCl)2 +X- (X = SbCl6 or FeCl4), F3CCSeNSeCCF3 +SbCl6 -, F3CCSeNSeCCF3, F3CCSeNSeCCF3 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3. Electron diffraction study...",
abstract = "Full title: 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. The salts N(SeCl)2 +SbCl6 - 1 and N(SeCl)2 +FeCl4 - 2 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 F3CCSeNSeCCF3 + SbCl6 - 3. 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 F3CCSeNSeCCF3 4, F3CCSeSeCCF3 5 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3 6. 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) {\AA}. In order to rationalize the structures of 5 and the cation F3CCSeNSeCCF3 +, ab initio calculations were made on model compounds in which the CF3 groups were replaced by a fluorine atom (i.e. FCSeSeCF for 5and FCSeNSeCF+ for the cation in 3). In addition, mass spectrometric experiments were performed in order to examine the structures and stabilities of the unligated cation F3CCSeNSeCCF3 + as well as its neutral counterpart. The existence of the neutral radical 4 was established by means of neutralization-reionization mass spectrometry.",
author = "Borisenko, {Konstantin B.} and Matthias Broschag and I. Hargittai and Klap{\"o}tke, {Thomas M.} and Detlef Schr{\"o}der and Axel Schulz and Helmut Schwarz and Tornieporth-Oetting, {Inis C.} and White, {Peter S.}",
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language = "English",
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journal = "Dalton Transactions",
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TY - JOUR

T1 - Preparation of N(SeCl)2 +X- (X = SbCl6 or FeCl4), F3CCSeNSeCCF3 +SbCl6 -, F3CCSeNSeCCF3, F3CCSeNSeCCF3 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3. Electron diffraction study...

AU - Borisenko, Konstantin B.

AU - Broschag, Matthias

AU - Hargittai, I.

AU - Klapötke, Thomas M.

AU - Schröder, Detlef

AU - Schulz, Axel

AU - Schwarz, Helmut

AU - Tornieporth-Oetting, Inis C.

AU - White, Peter S.

PY - 1994

Y1 - 1994

N2 - Full title: 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. The salts N(SeCl)2 +SbCl6 - 1 and N(SeCl)2 +FeCl4 - 2 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 F3CCSeNSeCCF3 + SbCl6 - 3. 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 F3CCSeNSeCCF3 4, F3CCSeSeCCF3 5 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3 6. 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 F3CCSeNSeCCF3 +, ab initio calculations were made on model compounds in which the CF3 groups were replaced by a fluorine atom (i.e. FCSeSeCF for 5and FCSeNSeCF+ for the cation in 3). In addition, mass spectrometric experiments were performed in order to examine the structures and stabilities of the unligated cation F3CCSeNSeCCF3 + as well as its neutral counterpart. The existence of the neutral radical 4 was established by means of neutralization-reionization mass spectrometry.

AB - Full title: 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. The salts N(SeCl)2 +SbCl6 - 1 and N(SeCl)2 +FeCl4 - 2 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 F3CCSeNSeCCF3 + SbCl6 - 3. 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 F3CCSeNSeCCF3 4, F3CCSeSeCCF3 5 and F3CCSeSeC(CF3)C(CF3)SeSeCCF3 6. 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 F3CCSeNSeCCF3 +, ab initio calculations were made on model compounds in which the CF3 groups were replaced by a fluorine atom (i.e. FCSeSeCF for 5and FCSeNSeCF+ for the cation in 3). In addition, mass spectrometric experiments were performed in order to examine the structures and stabilities of the unligated cation F3CCSeNSeCCF3 + 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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