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Pure Appl. Chem., 2012, Vol. 84, No. 11, pp. 2317-2324

http://dx.doi.org/10.1351/PAC-CON-12-02-14

Published online 2012-08-18

Synthesis and oxidation of hexafluoroisopropoxyborylferrocenes

Hannes Böhrer, Nils Trapp, Harald Scherer and Ingo Krossing*

Institut für Anorganische und Analytische Chemie, Freiburger Materialforschungszentrum (FMF) and Freiburg Institute for Advanced Studies (FRIAS), Section Soft Matter Science, Universität Freiburg, Alberstrasse 21, 79104 Freiburg, Germany

Abstract: The ferrocenylboranes (BOhfip2)Fc and 1,1'-(BOhfip2)2Fc were prepared (Fc = ferrocenyl, Ohfip = (CF3)2CH-O); 1,1'-(BOhfip2)2Fc was further oxidized giving [1,1'‑(BOhfip2)2Fc]+[Al(ORF)4] by oxidation of 1,1'-(BOhfip2)2Fc with Ag+[Al(ORF)4] (RF = C(CF3)3). Their X-ray crystal structures were determined and give further information on the Fe–B interaction through the dip angles α*. In [1,1'-(BOhfip2)2Fc]+[Al(ORF)4], this Fe–B interaction is enfeebled: the dip angles α* (0.3º and 5.4º) are significantly smaller than in (BOhfip2)Fc (7.8º) and 1,1'-(BOhfip2)2Fc (8.0º), and the hexafluoroisopropoxy moieties are twisted out of the Cp plane by up to 66.1º. NMR and vibrational spectra support the crystal structure assignments.