Synthesis and Fluxional Behavior of New "Haevy Fluorous" Cyclopentadienes.

0341109 - ÚCHP 2010 RIV CH eng J - Journal Article
Červenková Šťastná, Lucie - Čermák, Jan - Cuřínová, Petra - Sýkora, Jan
Synthesis and Fluxional Behavior of New "Haevy Fluorous" Cyclopentadienes.
Journal of Organometallic Chemistry. Roč. 695, č. 4 (2010), s. 537-545. ISSN 0022-328X. E-ISSN 1872-8561
R&D Projects: GA AV ČR IAA400720706; GA MŠMT(CZ) LC06070
Institutional research plan: CEZ:AV0Z40720504
Keywords : heavy fluorous * cyclopentadiene * polyfluoroalkylsilane
Subject RIV: CC - Organic Chemistry
Impact factor: 2.205, year: 2010

The new heavy fluorous cyclopentadienes C5H6-n[M(C2H4C6F13)3]n (M = Si, n = 1 (3); n = 2 (4) and M = Sn, n = 1 (10)) were synthesized by reaction of cyclopentadienyl lithium with BrSi(C2H4C6F13)3 (2) or BrSn(C2H4C6F13)3. Fluorous cyclopentadienes prepared in this manner contain three or six C6F13 groups, which significantly increase their solubility in perfluorinated solvents. They also provide intermediates for titanium complexes suitable for fluorous biphase catalysis. All three isomers of silylcyclopentadienes 3 and 4 were identified and fully characterized by two dimensional NMR spectroscopy, which was performed at low temperature. The allylic isomers 3a and 4a undergo degenerate metallotropic rearrangement. This fluxional behaviour was compared with the behaviour of previously prepared cyclopentadienes 6 and 7 (C5H6-n[SiMe2(C2H4C8F17)]n where n = 1, 2, respectively).
Permanent Link: http://hdl.handle.net/11104/0184195