From dihydropentafulvalenes to asymmetric biferrocene and terferrocene
摘要:
In order to realize a step-by-step synthesis of terferrocenes tetramethyldihydropentafulvalene has been mono-deprotonated and further converted to ferrocene and pentamethylferrocene which are both substituted by tetramethylcyclopentadiene (4 and 9, respectively). In these syntheses the intermediate half-sandwich (C5Me5)Fe(hfa)(MeCN) (hfa = hexafluoroacetylacetonate) proved to be a useful reagent. Compounds 4 and 9 could be deprotonated to corresponding ferrocenes which are substituted by tetramethylcyclopentadienyl anions (5 and 10, respectively). Anions 5 and 10 are building blocks for termetallocenes which has been demonstrated by the synthesis of octamethylated terferrocene from 5 and FeCl2. Tetradecamethylbiferrocene has been obtained by reaction of tetramethylpentafulvalene dianion with FeCl2. NMR features and redox properties of the new compounds have been analyzed. (C) 2001 Elsevier Science B.V. All rights reserved.