Intramolecular conversions of (aminoferrocenylpenta-1,4-dienyl)- ferrocenylcarbenes: Synthesis of diferrocenylmono-, bi-, tricycles and amino(diferrocenyl)hexa-1,3,5-trienes

Abstract

Synthesis of 3,4-diferrocenyltoluene (7), 1-morpholino- and 1-piperidino-2,3- diferrocenylbicyclo[3.1.0]hex-2-enes 8a, 8b, 1-morpholino- and 1-piperidino-7-ferrocenyl- 3,4-ferrocenobicyclo[3.2.1]oct-6-enes 9a, 9b, 2- and 3-amino(diferrocenyl)-hexa-1,3,5- trienes 10a,b, 11a,b by reactions of amino(diferrocenyl)cyclopropenylium tetrafluoroborates with 1-methylprop-2- enylmagnesium chloride at 80 °C is described. The structures of the compounds obtained were determined by IR, 1H- and 13C-NMR spectroscopy and mass spectrometry. X-ray diffraction data for 1-piperidino-7-ferrocenyl-3,4-ferrocenobicyclo[ 3.2.1]oct-6-ene (9b), 2-morpholino- and 2-piperidino-1,3-diferrocenyl-4-methylhexa- 1,3,5-trienes 10a and 10b is presented. The electrochemical behaviour of compounds 7, 8a, 10a and 10b was investigated by means of cyclic voltammetry and square wave voltammetry. For 7 and 8a two electrochemical processes (I-II), attributed to the oxidation of the ferrocene moieties were found. On the other hand for compounds 10a and 10b a single electron transfer for both ferrocene groups and the electrochemical generation of the monocation and dication species were detected. © 2011 by the authors; licensee MDPI, Basel, Switzerland.