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- Title
Reactions of Highly Branched Perfluoroolefins with (Pentafluorophenyl)trimethylsilane: Characterization of the Unique Structural Properties of Perfluorinated Super-Congested Systems.
- Authors
Nishida, Masakazu; Fukaya, Haruhiko; Hayakawa, Yoshio; Ono, Taizo; Fujii, Kotaro; Yasuda, Nobuhiro; Uekusa, Hidehiro
- Abstract
Hexafluoropropene trimers were reacted with C6F5Si(CH3)3 to provide not only pentafluorophenyl but also perfluorophenylene derivatives [F(C6F4) nC9F17; n=2-9] by successive pentafluorophenylation of perfluoroaryl rings. Their structures, including rotational isomers, were determined by MS, 19F and 13C-{19F} NMR spectroscopy, and/or X-ray crystallography, and were further confirmed by B3LYP-GIAO calculation of NMR shieldings. Formation of a pair of gear-meshed rotamers with clockwise and counterclockwise conformations was identified by NMR measurements for the structures having geminal (CF3)2CF groups at the C=C bond. That the predominantly formed counterclockwise rotamer was gradually converted to the clockwise rotamer over 50 days at room temperature through a synchronized movement of gears was also confirmed by NMR measurements. A comparison between the X-ray structure and B3LYP calculations showed some structural differences that arise from the crystal packing.
- Subjects
PERFLUORO compounds; ALKENES; TRIMETHYLSILYL compounds
- Publication
Asian Journal of Organic Chemistry, 2016, Vol 5, Issue 7, p927
- ISSN
2193-5807
- Publication type
Article
- DOI
10.1002/ajoc.201600167